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PALLADACYCLES
PALLADACYCLES
CATALYSIS AND BEYOND

Edited by

ANANT R. KAPDI
Department of Chemistry, Institute of Chemical
Technology, Mumbai, India

DEBABRATA MAITI
Department of Chemistry, Indian Institute of Technology,
Mumbai, India
Elsevier
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CONTRIBUTORS

Prachi Bangde
Department of Pharmaceutical Technology, Institute of Chemical Technology,
Mumbai, India
Bhalchandra M. Bhanage
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
Shatrughn A. Bhilare
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
Pui Ying Choy
Department of Chemistry, The Chinese University of Hong Kong, Shatin, Hong Kong
Prajakta Dandekar
Department of Pharmaceutical Technology, Institute of Chemical Technology,
Mumbai, India
Ian J.S. Fairlamb
Department of Chemistry, University of York, York, United Kingdom
Tejpalsingh R. Girase
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
Gaurav R. Gupta
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
Xinwei He
Department of Chemistry, The Chinese University of Hong Kong, Shatin, Hong Kong
Anant R. Kapdi
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
Raysa Khan
Department of Chemistry, School of Life Sciences, University of Sussex, Brighton,
East Sussex, United Kingdom
Fuk Yee Kwong
Department of Chemistry, The Chinese University of Hong Kong, Shatin, Hong Kong
Fátima Lucio-Martı́nez
Departamento de Quı́mica Inorgánica, Universidad de Santiago de Compostela, Santiago de
Compostela, Spain
Debabrata Maiti
Department of Chemistry, Indian Institute of Technology, Mumbai, India
Helena C. Malinakova
Department of Chemistry, The University of Kansas, Lawrence, KS, United States

ix
x Contributors

M. Teresa Pereira
Departamento de Quı́mica Inorgánica, Universidad de Santiago de Compostela, Santiago de
Compostela, Spain
Dharmendra Prajapati
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
Benudhar Punji
Organometallic Synthesis and Catalysis Group, Chemical Engineering Division,
CSIR–National Chemical Laboratory (CSIR–NCL), Pune, India
Francisco Reigosa
Departamento de Quı́mica Inorgánica, Universidad de Santiago de Compostela, Santiago de
Compostela, Spain
Jose L. Serrano
Department of Mining, Geological and Cartographic Engineering, Inorganic Chemistry
Section, Technical University of Cartagena, Regional Campus of International Excellence
“Campus Mare Nostrum”, Cartagena, Spain
Jagrut A. Shah
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
Kevin H. Shaughnessy
Department of Chemistry & Biochemistry, The University of Alabama, Tuscaloosa,
AL, United States
Vineeta Soni
Organometallic Synthesis and Catalysis Group, Chemical Engineering Division,
CSIR–National Chemical Laboratory (CSIR–NCL), Pune, India
John Spencer
Department of Chemistry, School of Life Sciences, University of Sussex, Brighton,
East Sussex, United Kingdom
Jose M. Vila
Departamento de Quı́mica Inorgánica, Universidad de Santiago de Compostela,
Santiago de Compostela, Spain
CHAPTER 1

Palladacycles as Efficient
Precatalysts for Suzuki-Miyaura
Cross-Coupling Reactions

M. Vila, M. Teresa Pereira, Fátima Lucio-Martínez,
Jose
Francisco Reigosa
Departamento de Quı́mica Inorgánica, Universidad de Santiago de Compostela, Santiago de Compostela, Spain

Contents
1. Introduction 1
2. Imine and Amine Palladacycles 3
3. Oxime Palladacycles 5
4. Ferrocene Palladacycles 6
5. Pincer Palladacycles 9
6. Phosphorus Donor Atom Palladacycles 10
7. Carbene Palladacycles 12
8. Alternative Palladacycles 13
9. Conclusions 16
References 17

1. INTRODUCTION
Palladacycles (1–5) are a paramount class of organometallic compounds
which, over recent years, have arisen as valuable devices in the preparation
of organometallic substances, especially in cross-coupling processes lead-
ing to the formation of carbon-carbon bonds, namely the Suzuki-Miyaura
reaction (6–10). Palladacycles constitute the precatalysts that provide the
necessary palladium itself in an oxidation state dependant on the proposed
catalytic cycle, i.e., Pd(0)/Pd(II)//Pd(II)/Pd(IV), or alternatively, where
palladium intercedes in the course of the reaction, more often than not
palladacycles emerge as intermediates. Well known reasons for their ample
use in such performances are, among others, that they are fairly stable and
that with few exceptions may be readily prepared in reasonably good
yields. After the pioneering work by Herman et al. (11–13) involving

Palladacycles © 2019 Elsevier Inc.

https://doi.org/10.1016/B978-0-12-815505-9.00002-0 All rights reserved. 1
2 Palladacycles

Scheme 1.1 The Suzuki-Miyaura cross-coupling reaction.

phosphine palladacycles, countless amounts of new palladacycles have

been tested for this purpose.
The Suzuki-Miyaura process consists in the cross-coupling reaction of
organoborated compounds (Ar1-B(OR)2) with electrophiles (Ar2-X) cata-
lyzed by palladium (14, 15). This is one of the most efficient methods for
making carbon–carbon bonds between aryl rings (Scheme 1.1).
Precisely, one of the main advantages of the Suzuki-Miyaura reaction is
that it uses organoborated species as precursors; in particular, various reac-
tions have been carried out with organoborated derivatives, such as esters of
boronic acids and alkylboranes. Another important aspect is the possibility of
using water as solvent (16, 17). Because water is an excellent solvent for
microwave heating, the combined use of water as solvent plus heating by
microwave radiation has also been considered (18). It is generally accepted
that the catalytic cycle for the Suzuki–Miyaura reaction is initiated with an
oxidative addition of the electrophile (Ar2-X) to the catalyst generating the
intermediate {Ar2-[Pd]-X}. The resulting complex undergoes transmetalla-
tion between {Ar2-[Pd]-X} and (Ar1-B(OH)2) to give the disubstituted
palladium species {Ar1-[Pd]-Ar2}, after which reductive elimination of
the palladium-disubstituted moiety occurs, releasing the coupling product
(Ar1-Ar2) and regenerating the catalyst, which is incorporated again into
the cycle; the latter step verifies the catalytic efficiency of the palladacycle
(Scheme 1.2).

Reductive elimination Oxidative addition

Transmetallation
Scheme 1.2 The Suzuki-Miyaura catalytic cycle.
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 3

The amount of references, inclusive of reviews, related to palladacycles

that have been used in the aforementioned process is overwhelming. So,
far from being comprehensive on this issue, the reader may find an account
of the most outstanding aspects of this chemistry as from the work of
Dupont (3) and Bedford (Chapter 8 in (2)). Also, despite strict frontiers
between the palladacycles sometimes being difficult to define with preci-
sion, herein they are mainly classified as a function of the nature of the
metallated ligand.

2. IMINE AND AMINE PALLADACYCLES

This is a rather large group of palladacycles owing to the accessibility of the
amine ligands and to the ease of the preparation of Schiff bases aka imines.
Yang et al. showed that Shiff base palladacycles bearing arsines or stibines 1
were good catalysts for the Suzuki-Miyaura cross-coupling between aryl-
boronic acids and aryl bromides, with yields c.90%.

However, for the analogous aryl chloride or chloronitro derivatives the

result was c.30% or lower. Attempts to perform the reaction in aqueous
media produced only traces of the coupled products (19). Similar mononu-
clear palladacyles, albeit coordinated to tertiary phosphines, were success-
fully tested by Serrano et al. for the reaction between benzyl bromide
and arylboronic acids with yields >70%, which proceed with formation
of a Pd0(PR3) intermediate (20). Nitrogen donor palladacycles have been
used in aqueous-biphasic solvent systems in order to obtain a recyclable cat-
alytic system. The hydrophilic palladacycles 2, prepared from p-hydroxy-
benzylamine, and 3, from a sulfonated imine produced active catalysts
for the cross-coupling of aryl bromides combined with t-Bu-Amphos
(21). The 3/t-Bu-Amphos system was shown to be greatly recyclable, with
yields above 86% and a life span of twelve cycles.
4 Palladacycles

Similar Schiff base palladacycles (22) showing air and moisture insensitiv-
ity were inspected for the Suzuki-Miyaura coupling reaction between aryl
halides and arylboronic acids. For example, complex 4 displayed an activity
of up to TON c.107, it being suggested that palladacyclic catalysis was via pal-
ladium nanoparticles. Furthermore, the catalytic activity of amine N-donor
palladacycles may be enhanced by supporting the catalyst over graphene
oxide (23); the resulting nanohybrid system 5 shows a TON of 80,000
and a TOF (h
1) of 240,000. Other more sophisticated amine N-donor pal-
ladacycles have been applied as catalysts. Thus, the bulky pisdene complex
6 (pisdene ¼ 3-benzyl-7-methyl-3,7-diazabicyclo[3.3.1]nonane) displayed
an 85% yield under mild conditions for the cross-coupling between
4-bromoanisole and phenylboronic acid (24); while the tetranuclear pallada-
cycle 7 was an air stable catalyst with a TON as high as 228  103 with a
catalyst mol percentage of only 390  10
6 (25). Phenylalanine palladacycles
8 may lead to polymer-type species as in the Suzuki cross-coupling polymer-
ization of dibromides with diboronic acids with shorter reaction times than
other conventional palladium catalysts (26). Pyridinium salts related to those
in ionic liquid solvents withstand palladation as well to produce palladium-
pyrilydene compounds 9 as active catalysts for the Suzuki reaction (27).
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 5

3. OXIME PALLADACYCLES
The related oxime palladacycles have been shown to be likewise effective for
the Suzuki coupling (28). They furnish the origins of remarkably effective
compounds that allow for less rigorous reaction conditions. Oximes of the
type 10 have been successfully applied to the cross-coupling reaction of even
sterically impeded and deactivated aryl chlorides in water using microwave
heating (29–31). The “light fluorine” containing dinuclear oxime palladacycle
11 (fluorine content less than 50%) with two perfluoro octyl groups attached is
very active for promoting the Suzuki reaction in aqueous media, with very
low palladium leaching, as well as the use of microwave heating (32).

Oxime-based palladacycles have also been used as heterogeneous cata-

lysts. An alcoxy oxime palladacycle resin 12 was tested for the Suzuki reac-
tion. Microwave radiation improved its activity for the coupling of
4-bromoanisole with phenyboronic acid under 20 minutes with a yield
greater than 94% (33, 34).

Fixing the catalyst on polyvinylpyridine (PVP) resin affords a reusable,

air, moisture, and thermally stable palladium precatalyst 13, which shows
6 Palladacycles

low intensity leaching and that is suitable for continuous flow operations
(35). Nájera et al. (36) have evaluated the effectiveness of the Kaiser
oxime-based palladacycle 14 with K2CO3 as base in water under reflux
for the coupling between phenylboronic acid and several substituted aryls,
among others, with yields >90%. Poorer results were obtained for alkyl
boronic acids, but diverse styrenes and stilbenes were prepared using this cat-
alyst. Other alternatives include, for example, oxime palladacycles supported
on graphene oxide (37) (vide supra), which are most convenient for the reac-
tion between aryl bromides and arylboronic acids working with little catalyst
quantities in water at c.25°C. Other materials available for supporting oxime
palladacycle precursors 15 developed by Corma et al. (38) include mesopor-
ous silica yielding an heterogeneous catalyst.

Moreover, a mini review concerning oxime palladacycles as catalysts not

only in the Suzuki-Miyaura coupling, but in other in carbon-carbon bond
formation processes as well, has recently been given by Nájera (39).

4. FERROCENE PALLADACYCLES
A wide variety of ferrocene derivatives has been researched by Wu et al. The
ferrocenylimine palladacycle 16 was an advantageous catalyst for the cross-
coupling of 3-pyridylboronic pinacol ester with an assortment of iodide,
bromide, and the electron-rich chlorides (40). Reasonable to good yields,
close to or above 96%, were obtained for catalysis of 3-pyridin boronic pina-
col ester with aryl iodides. Lower yields were obtained in general for the
analogous bromide derivatives. Also, the catalyst proved to be rather effi-
cient in the cross-coupling of aryl chlorides with yields reaching 80% using
cesium carbonate as base. Reduction of the C]N double bond with
NaBH4 or with LiAlH4 gives the related ferrocenylamine palladium com-
plexes 17 (41) and 18 (42) which are also quite suitable catalysts. The latter
presents two pairs of racemates RnRp/SnSp and SnRp/RnSp. The corre-
sponding carbene adducts have also been examined and they have success-
fully been employed in the Suzuki coupling (43).
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 7

Triscyclohexylphosphine or 2-(dicyclohexylphosphanyl)-20 -(dimethyla-

mine)biphenyl as ancillary ligand in the mononuclear air-stable palladacycles
20 (44) and 21 (45), respectively, enhances the activity of the catalysts. It
has been shown that compound 20 with R1 ¼ Me, R2 ¼ p-MeC6H4, is
highly efficient for borylation catalysis to give unsymmetrical biaryls (46).

Analogues of 20 are quite adequate for binding the CF3CH2 moiety to an

aromatic ring (47), albeit that the yields are far from high ranging roughly ca.
40%–50%, as well as for couplings between boronic acids and carboxylic
anhydrides or acyl chlorides (48).
In order to avoid the use of cumbersome bulky phosphines, these may be
substituted by pyridine to produce phosphine-free catalysts 22 (49) which
8 Palladacycles

display quite high yields in the Suzuki reaction. Other phosphine-free

palladacycles (50) prepared from ferrocenylimidazolines have been inves-
tigated as catalyst showing good to excellent results. Complexes of type
23 may give yields >95% for cross-coupling of aryl bromides with phenyl
boronic acid, and for those cases where the choice of the halide deri-
vative was the corresponding chloride, the resulting yields were in the
range 51%–88%, with a peak at 97% when 24 (51) was employed in
the coupling with 4-nitrochlorobenzene. The Suzuki reaction may be
used to synthesize polydentate palladacycles. This may be achieved by
cross-coupling on the ligand itself, which is then metallated; or alterna-
tively, the ferrocene palladacycle 25 is made first and then it undergoes
the Suzuki coupling with the appropriate biphenyl boronic acid (52).
Whichever is the case, the final product is 26; however, by the second
pathway the reaction can proceed without addition of a second palladium
source as catalyst.

Terdentate [C,N,E] (E ¼ S, Se) ferrocenylimine palladacycles 27 (53)

have been explored for the Suzuki-Miyaura reaction between arylboronic
acids and an array of substituted aryl chlorides and bromides yielding satis-
factory results, with the selenium derivative being somewhat more powerful
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 9

than the sulfur analogues. Half-sandwich cyclopentadienyl metal moieties as

a fundamental part of the palladacycle have been invoked as potential cata-
lysts in the Suzuki cross-coupling reaction, for example the dinuclear Re/Pd
complexes described by Gladysz et al. (54) 28 and 29, albeit conclusive
experiments, still remain outstanding.

5. PINCER PALLADACYCLES
Pendant benzamidinate palladacycles are good catalysts for the Suzuki cou-
pling, with those having the oxazoline group 30 showing greater activities
than those with pyridine or amine group (55). In this case, lower loadings
may be used and the conversion, as followed by 1H NMR, is up to 99% with
an isolated yield of 92%. Palladacycles with phosphaalkene ligands 31 (56),
or with nitrogen and selenium or sulfur donors 32 (57, 58) give air stable
catalysts with TONs of 93,000 and the conversion to nano-sized particles
Pd17Se15, is believed to be the real active species.

The critical role of nanoparticles has also been invoked in the case of
phosphine-free palladacycles with selenium donors such as 33 where
Beletskaya et al. (59) provide a critical point of view related to this issue,
while pursuing evidence on the nanoparticle-enabled route as opposed
to the mononuclear route. Nonsymmetrical [N,C,N], [N,C,P] and
10 Palladacycles

[N,C,S] palladium pincer complexes such as 34 (60), 35 (61), 36 (62),

proved to be highly efficient catalysts with yields of nearly 100% in
the cases of 34 and 36. Other unsymmetrical [C,N,N] high performing
palladacycles containing iminopyridyl 37 (63) have been developed by
Hu et al. for the synthesis of 1,1-diarylalkanes for coupling of benzylic
bromides with arylboronic acids with substantial selectivity and TON
of 47,000.

6. PHOSPHORUS DONOR ATOM PALLADACYCLES

Polystyrene supported adducts of amine and phosphite palladacycles have
been used as catalysts in the Suzuki reaction for aryl chlorides (64). Con-
finement of the catalyst in the polystyrene base may lead to enhanced
performance when matched against their homogeneous counterparts.
However, the supported catalysts may not be recovered. Better conver-
sion in terms of TON was obtained in one reaction for 38. In contrast,
the carbene and phosphine adducts of similar phosphite and phosphinite
palladacycles 39 for coupling of alkyl bromides with phenyl boronic acid
showed poor results (65). No improvement with respect to other palla-
dium sources, such as palladium acetate, was found. Furthermore, it seems
at this point that the oxidative addition of the alkyl halide is not the rate
determining step.
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 11

A palladacycle giving very high activity in aqueous media at ambient

temperature 40 has been devised using an upgraded protocol, selected from
amongst a series of related phosphorus donor compounds and tested to give a
91% yield (66). An improved protocol employing 41 in aqueous media was
achieved avoiding use of organic solvents, with isolated yields of 99% in
some cases (67). Initial treatment of the catalyst with boronic acid shortens
the reaction times.

Dinuclear phosphorus donor palladacycles are also useful catalysts (68, 69).
The palladation of the biphenylphosphine Ph2P{2-(2-MeC6H4)C6H4} gave
42 as a water soluble complex. This palladacycle was remarkably valid for
the coupling between aryl halides and phenylboronic acids producing yields
of 100% with TON of 100,000. Phosphite palladacycles may be applied to
the preparation of fluorenones (70). Thus, compound 43 catalyzes the addition
reaction between arylboronic acids and halogen containing aromatic aldehydes
that, after cyclization, renders fluorenones and indenofluorenediones. The
related palladated phosphites 44 can be utilized for the carbonylative
Suzuki-Miyaura cross-coupling of aryl iodides with boronic acids to give biaryl
ketones (71). The numerous coupling reactions show turnover numbers and
turnover frequencies spreading over 106–107 and 105–106 h
1, respectively.
12 Palladacycles

Finally, palladacycle ylides 45 (72, 73) have been submitted to the Suzuki
coupling reaction of aryl chlorides and bromides with good to excellent
results; yields ranging c.70%–85%.

7. CARBENE PALLADACYCLES
Carbene palladacycles as catalysts for the Suzuki-Miyaura coupling have
emerged in the past as a strong challenge to the widely employed phosphine
complexes. The carbene ligand is a firm σ donor and the resulting complexes
enjoy flexibility and firmness of the molecular architecture. Nolan (74) has
given a general overview regarding palladium-carbene compounds suitable
for cross-coupling reactions, inclusive of a section dedicated to the pallada-
cycles. Since then, a good number of papers have appeared in relation to
these catalysts, which we will briefly comment on herein.
Complexes of type 46, 47 (75) and 48 (76) have been shown to be first-rate
catalysts for the Suzuki coupling with more or less activated aryl bromides
against phenylboronic acids even at low catalyst loadings; 46 being more active
than 47, consequent on the greater stability of the former. The methyl groups
on the benzimidazole in 48 play a determining role in enhancing the activity of
the catalyst. In all cases, yields ranging c.85%–95% were achieved.
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 13

Ying et al. (77) have described a differing library of palladacycles, for

example 49, prepared in a novel fashion, consisting in the heating of imida-
zolium salts with adequate acetate palladacycles, for the cross-coupling
between deactivated aryl chlorides and phenylboronic acid under smooth
reaction conditions. The bulky carbene substituents are paramount in
expanding the catalytic ability. Later, Zhang et al. (78) implemented this
and other palladium complexes on the surface of hydrophobic mesoporous
ethane-silica gel 50 making a solid phosphine-free catalyst applicable to the
Suzuki coupling even in the case of the less activated aryl chlorides. The
inclusion of the azide ligand in the palladacycle 51 (79) seems to improve
the catalytic quality of the corresponding species, as opposed to the analo-
gous chlorides, with yields c.99% in some cases.

Kapdi et al. (80) described the preparation of carbene palladacycles 52, 53

derived from dinuclear hydroxy-bridged palladium complexes, that are most
suitable for the arylation of 9-bromophenanthrene with a wide variety of
arylboronic acids. The yields in the pertinent conditions are up to 96%.

8. ALTERNATIVE PALLADACYCLES
Further examples of palladacycles that could well fit into several of the cat-
egories described above will be now mentioned. Mono- and dinuclear pal-
ladacycles exhibiting [S,C] 54 and [S,C,C] 55 coordination have been found
14 Palladacycles

to be active catalysts (81); the latter present σC2sp-Pd and σC3sp-Pd bonds on
the same compound. The mononuclear [S,C] bonded complexes display
greater activity in the Suzuki coupling tests. The related palladacycles
derived from benzamidines with pendant thioether groups (82), showing
[C,N,S] coordination 56, have also displayed a significant activity for the
Suzuki coupling reaction.

Treatment of dinuclear six-membered [C,N] guanidine palladacycles with

bridging halide ligands (Cl, Br) with dimethyl pyrazole gave mono-nuclear
complexes after halide substitution to render active catalysts for the cross-
coupling reaction between phenylboronic acid and 4-bromotoluene; namely
57 showed a yield of 100% and TON of 100 (83). Dunina et al. (84) studied the
competition of two catalytic cycles in the Suzuki coupling process by probing
various palladacycles in protic and aprotic media, especially in the cases of
metallated cyclophane Schiff base ligands. For instance, complex 58 concurs
mainly with the Pd(II)/Pd(0) pathway and leaves the palladacycle framework
practically intact.

Indole based [C,N,N] palladacycles (85) with a pincer-type arrange-

ment 59 or with spiro chelating rings 60, possessing one or two metal
centers, respectively, or alternatively the terdentate [C,N,N] triphenyl-
pyrazole derivatives 61 (86), have been shown to be highly active
catalysts.
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 15

From the foregoing, it can be stated that we are not far from the truth if
we say that actually any palladacycle may be used as catalyst more or less
effectively in the Suzuki–Miyaura reaction. After all, palladacycles are really
precatalysts which liberate Pd(0), or in any case "active palladium" in the
media. The question stands as, can we perform this reaction without addi-
tion of a palladium source as catalyst? Recently, the Vila group (87) has
answered this by showing that if the Suzuki-Miyaura carbon-carbon bond
formation reaction takes place solely on the palladacycle, it may proceed in
the absence of addition of a "traditional" palladium catalyst, such as for
example Pd(PPh3)4, or of an appropriate palladacycle. This suggests that it
is the functionalized palladacycle itself 62 that plays the role of the catalyst;
it simultaneously holds the precatalyst and the boronic function. The ade-
quately functionalized palladacycle auto-directs an aryl ketone halide pro-
ducing an autocatalytic operation with formation of the carbon–carbon
bond to give 63, Scheme 1.3.
The catalytic cycles may involve either Pd(0)/Pd(II) or Pd(II)/Pd(IV)
mechanism, with the former being more often than not invoked as it implies
release of Pd(0) in the reaction medium. However, in this case the initial

Scheme 1.3 Formation of 63 via autocatalysis from 62.

16 Palladacycles

Scheme 1.4 Proposed Pd(II)/Pd(IV) mechanism for the Suzuki-Miyaura cross-coupling

of 62 to 63. 1: Oxidative addition; 2: Transmetallation; 3: Reductive elimination.
L ¼ PPh3.

palladium oxidation state, Pd(II), on the one hand, and the strength of the
bonds at the metal imposed by the strongly chelating thiosemicarbazone
ligand, on the other, is surely in favor of the latter mechanism. This is what
was proposed by Vila et al., and further confirmed by DFT calculations on
species in the cycle (Scheme 1.4).

9. CONCLUSIONS
In recent publications that include palladacycles, or other metallic com-
pounds, for that matter, that act as catalysts when cross-coupling reactions
are considered, it can be seen that the number of species is increasingly
numerous. The figures depicted in this chapter are only the tip of the iceberg
in what relates to the tremendous variability of complexes that have been
applied to the Suzuki-Miyaura coupling reaction, an endless myriad of more
 Palladacycles as Efficient Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions 17

or less efficient catalysts. It would seem, however, that there are much more
simple compounds, such as PdCl2, Pd(AcO)2 or Pd(PPh3)4, which can act as
excellent catalysts and which are commercially available, thus avoiding the
often tedious and low-yield work of preparing the more complex species
mentioned; it would not make much sense to continue researching to obtain
compounds of the type discussed above. One author of such species, Belets-
kaya (8) stated some time ago that, in relation to the particular case of palla-
dacycles as catalysts "after a survey over the application of palladacycles in catalysis it
becomes evident that the initial are often announced as outstanding because of very
high catalytic activity in several test reactions, very rarely find applications in prepar-
ative chemistry. Neither enantioselectivity nor recyclability has been realized. Dozens
of palladacycles of all imaginable classes have been studied in various cross-coupling
reactions, but none appeared to be the “well-defined catalyst”, which has been the
initial leitmotiv of this story."
The literature illustrates that the search for new catalysts continues to
resolve aspects such as the improvement of the effectiveness of the catalyst
in terms of its performance and TON, its recoverability, lower working
temperature, water soluble catalysts, possibility of application to multiple
processes, industrial uses …, in short, an ideal catalyst that compensates
for the synthesis of sophisticated metal compounds, in particular the
palladacycles.

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CHAPTER 2

Palladacycles as Precatalysts
for Heck and Sonogashira
Cross-Coupling Reactions
Pui Ying Choy, Xinwei He, Fuk Yee Kwong
Department of Chemistry, The Chinese University of Hong Kong, Shatin, Hong Kong

Contents
1. Introduction 21
2. Phosphine-Based Palladacycles 23
2.1 Heck Cross-Coupling Reaction 23
2.2 Sonogashira Cross-Coupling Reaction 37
3. Ferrocene-Based Palladacycles 47
3.1 Heck Cross-Coupling Reaction 47
3.2 Sonogashira Cross-Coupling Reaction 57
4. Amine/Imine/Oxime-Based Palladacycles 60
4.1 Heck Cross-Coupling Reaction 61
4.2 Sonogashira Cross-Coupling Reaction 82
5. N-Heterocyclic Carbene-Based Palladacycles 94
5.1 Heck Cross-Coupling Reaction 95
5.2 Sonogashira Cross-Coupling Reaction 115
6. Pincer-Based Palladacycles 122
6.1 Heck Cross-Coupling Reaction 123
6.2 Sonogashira Cross-Coupling Reaction 144
7. Other Palladacycles 153
7.1 Heck Cross-Coupling Reaction 153
7.2 Sonogashira Cross-Coupling Reaction 157
8. Conclusions and Prospects 161
References 162

1. Introduction
The palladium-catalyzed Heck reaction was firstly discovered in the late
1960s and remains one of the most valuable and prominent strategies to syn-
thesize complex carbon molecules (1). This reaction aims to connect arene
and olefin fragments together via a transition metal-catalyzed reaction

Palladacycles © 2019 Elsevier Inc.

https://doi.org/10.1016/B978-0-12-815505-9.00003-2 All rights reserved. 21
22 Palladacycles

pathway. In 2010, Prof. Richard F. Heck was recognized by the Nobel Prize
in Chemistry for his pioneering invention and the exceedingly significant
contribution of this reaction (2). In fact, the versatility of this cross-coupling
process has been demonstrated in the pharmaceutical, agricultural, and elec-
tronics synthesis (3). This chemistry offers excellent opportunity in develop-
ing new fields of research, and provides a solid platform for convergent
organic synthesis (4). Sonogashira cross-coupling reactions is the direct cou-
pling of terminal alkyne CdH bond with electrophilic aryl halides (5,6).
This method features a modular approach in preparing an array of diversified
aryl alkynes and conjugated enynes, which are important synthetic precur-
sors for a range of pharmaceutically attractive intermediates and subunits of
materially valuable organic compounds (7). These two coupling reactions
have been extensively studied and their related topics such as the applica-
tions, techniques, and mechanism have also been reported (8). Apart from
those reviews, there are a few literatures that illustrate a general overview of
the catalyst design toward these reactions.
Palladacycles have emerged as a complimentary family of organopalla-
dium catalysts (or catalyst precursors) for many CdC and CdX (where
X ¼ N, O, S, P) cross-coupling reactions. The first cyclopalladation was dis-
covered in the 1960s by Cope (9) and the palladacyclic catalyst has become
one of the most popular catalysts used for the Mizoroki-Heck type reactions
in recent years. The general structures of the palladacycles can be categorized
into two main classes with two subareas: 1st class) anionic four/six-electron
donor palladacycles—(A) the simple palladacycles with one ligand coordi-
nation to the palladium species in a ĸ2-L,C manner to form a stable, five/
six membered ring (C-L type) and (B) “pincer” palladacycles in which
the metallated carbon is supported by two donors in a ĸ3-L,C-L manner
(L-C-L type); 2nd class) the palladacycles exist as halogen or acetate bridged
dimers, with cis- or trans-conformations.
In the past decade, palladacycles have received increasing attention
because of their unique structure, chirality in the metallocene series, and
their superior catalytic activities in many organic transformations (10).
The landmark employment of palladacycles in cross-coupling reactions
occurred in the late 1990s with the introduction of Herrmann-Beller’s cat-
alyst. Since then, a wide variety of palladacycles have been reported, such as
phosphorus-, ferrocenyl-, nitrogen-, NHC-, pincer-, and sulfur-based pal-
ladacycles. For brevity, we herein focus on the recent developments in the
past decade with these palladacycles in the Heck and Sonogashira cross-
coupling reactions. Not surprisingly, there is overlap between sections;
 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 23

many publications reported more than one class of palladacycles and many
palladacycles contain more than one class of structures (e.g., both P and
N-donor atom exist in the same palladacycle). Numerous reviews and book
chapters have been written covering the literature, and a selection of the
publications will be appraised.

2. Phosphine-Based Palladacycles
Palladacycles serving as the catalysts in cross-coupling reactions appeared in
1995 (11). The Herrmann-Beller’s catalyst (1) is a very effective catalyst/
promoter for the Heck and Sonogashira coupling reactions. With the suc-
cessful examples of 1, different phosphorous-derived palladacycles were
developed and named “phosphapalladacycles” (12). There are two major
approaches for modifying phosphapalladacycles: (1) modification of the
electronic and steric properties; and (2) alternation of the nature of the aux-
iliary ligands in the coordination environment of palladium (13). In general,
the palladium is bound directly to one or two phosphorus(III) atom(s) and to
one carbon-anionic center (bi- or tridentate ligand chelation). They are sim-
ply illustrated as PC- and PCP-type cyclopalladated complexes, respectively.

2.1 Heck Cross-Coupling Reaction

2.1.1 Herrmann-Beller-Type Palladacycles
The representative “Herrmann-Beller’s catalyst” exists in the form of acetate-
bridged dimer. It is capable of dealing with the Heck reactions between a wide
variety of aryl halides and styrene/acrylate (Table 2.1). TBAB was added to
further promote the coupling reaction when difficult aryl chlorides were
used as the coupling partners. LiBr, [AsPh4]Cl, [PPh4]Cl and Bu4NClH2O
are other alternatives of additives (16). Although the catalyst system was able
to facilitate this reaction, high reaction temperature (130–160°C) was found
to be necessary.
Detailed mechanistic studies and kinetic modeling investigations were
carried out by B€ ohm, Herrmann (18) and Blackmond, and Pfaltz (19). The
reaction rate is highly dependent on the catalyst preactivation step. The
kinetic model of the Heck coupling between bromobenzaldehyde and
n-butyl acrylate showed that the catalytic efficiency increased at lower catalyst
concentration. Later, de Vries further indicated that Pd(0) black was formed at
high Pd concentration. A kinetic study was carried out to compare the kinetic
behavior of palladacycles and a homeopathic ligand-free palladium catalytic
system. The results showed that the resting state of the catalyst within the
 24
Palladacycles
Table 2.1 Herrmann-Beller’s catalyst (1) in Heck reaction

Entry 1 (mol% Pd) ArX R Time (h) Solvent Additive Yield (%) Ref.
1 2.0 C6H5Br CO2n-Bu 48 DMA — 96 11
2 1.0  103 p-CHOC6H4Br CO2n-Bu 12 DMA — >99 11
3 2.0 o-MeC6H4Br CO2n-Bu 48 DMA — 92 14
4 0.1 p-n-BuC6H4Br Ph 15 TBAB — 83 15
5 0.2 p-CHOC6H4Cl CO2n-Bu 24 DMA TBAB 81 11
6 0.1 p-CNC6H4Cl Ph 68 DMA TBAB 48 14
7 1.0 p-CF3C6H4Cl Ph 15 TBAB LiBr 91 15
8 2.0 C6H5Cl Ph 16 TBAB [AsPh4]Cl 96 16
9 4.0 p-MeOC6H4Cl Ph 14 TBAB [PPh4]Cl 18 16
10 0.2 o-CNC6H4Cl Ph 24 DMA Bu4NClH2O 94 17
 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 25

catalytic cycle is the intermediate derived from oxidative addition, and the
proposed catalytic cycle is depicted in Fig. 2.1 (20). In general, the bromoar-
enes undergo an acetate/bromide exchange at the beginning of the coupling
reaction and a Pd(II)–Pd(IV) cycle was proposed (11). In 2001, a detailed
investigation was carried out about the influence of the reaction conditions
in the Heck coupling of 1-chloro-4-trifluormethylbenzene using pallada-
cycle 1 (17). The basicity, additive, and solvent are all important factors to
the success of this reaction. Other kinetic studies were further performed
and they were in good agreement with the mechanism suggested by Black-
mond and Pfaltz (21).

Fig. 2.1 Proposed catalytic cycle by Blackmond and Pfaltz.

Methacrylic acid derivatives are common reagents for the Heck reac-
tions. Beller and co-workers have pioneered the use of 1 for the coupling
of aryl bromides with the alkyl methacrylate. With the standard reaction
conditions, a mixture of products was formed including the C]C double
bond isomers as well as the doubly arylated products. By detailed screening,
the selectivity of the reaction is highly influenced by the nature of the base
(22). The same group further tested the selectivity of Heck reactions of aryl
bromides with cyclohexene in 1999 (Scheme 2.1) (23). Mixture of isomers
was obtained and it showed that the double-bond migration was catalyzed
slowly by the base but not by HPdX complex.
26 Palladacycles

Scheme 2.1 Mixture of isomers formed by Heck reaction between aryl bromide and
cyclohexene.

Herrmann-Beller’s catalyst is a well-established precatalyst for the gen-

eral Heck coupling reactions. Recently, chemists moved forward to employ
this notable catalyst to other interesting Heck-related reactions. An inter-
and intramolecular double Heck coupling of bridged o,o0 -dibromobiaryls
with ethyl acrylate was demonstrated in the presence of Herrmann-Beller
catalyst (Scheme 2.2) (24).

Scheme 2.2 Double Heck reaction of bridged o,o0 -dibromobiaryls.

Alkyl acrylates are usually employed as the model substrates for initial
investigation of the Heck process. Djakovitch group expanded the scope
of this reaction to acrolein (25). Selective cinnamyl derivatives or double-
arylated products could be afforded depending on the catalyst, the base,
and the solvent used. In the presence of 1, NaOAc as the base and DMA
as solvent, 33% of the mono-arylated products in conjunction with 25% of
the β,β-diarylated products were given. However, 89% of the mono-arylated
products and only 5% of diarylated products resulted when NMP solvent was
used. Djakovitch further applied palladacycle 1 in the Heck arylation of
diethyl vinylphosphonate. It is an important exploration that polymerization
of acrolein often results instead of the desired products by using common
palladium catalyst system. Acrolein diethyl acetal is alternatively used instead
of acrolein to avoid possible polymerization problems. Saturated esters or
α,β-unsaturated aldehydes could be given as the products (Scheme 2.3).
Interestingly, when aryl iodide was coupled with acrolein diethyl acetal using
the same catalytic system, except water was used as the solvent, no saturated
esters but only α,β-unsaturated aldehyde was afforded (26). In 2014, Larhed
demonstrated a microwave-heated continuous-flow system for the Heck
coupling of aryl bromides and substituted n-butyl acrylate using palladacycle 1
(27). It was noted even for large-scale synthesis.
 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 27

Scheme 2.3 Herrmann-Beller’s catalyst in Heck arylation of acrolein and its derivatives.

Herrmann-Beller’s catalyst is a representative precatalyst which can be

used for genuine application of organic synthesis. Through an intra- or
intermolecular or double Heck coupling, intermediates of some useful
materials can be accessed for further transformations (Scheme 2.4) (28).
Fluorous ponytail-substituted aromatics are useful building blocks for the
construction of functionalized soluble ligands. In order to synthesize these
fluorous ligands with ethylene spacers, the Heck reaction using
Hermann-Beller’s catalyst is one of the possible methods (29). Sj€ oberg
and co-workers employed phosphapalladacycle 1 in the vinylation of
2-iodo-p-carborane which can be used as hydrophobic pharmacophores
(30). The catalyst 1 allowed the Heck arylation at C-8 of adenine nucleo-
sides which is an important medicinal and biological active unit (31).
A small amount of cis-isomer was detected and the trans-olefin was afforded
as the major product. An intramolecular Heck cyclization of protected
amines was successfully achieved with 1 for synthesizing useful
phenanthridine-incorporated alkaloid frameworks (32). A highly diaster-
eoselective construction of tetracyclic steroid core was established with a
two-fold Heck reaction and the unnatural cis-product can be further con-
verted into orally contraceptive desogestrel by common methods (33). The
Stewart group reported the synthesis of N-heterocycles by a series of dom-
ino reactions having the key Heck reaction with Herrmann-Beller’s cat-
alyst system (34).
28 Palladacycles

Scheme 2.4 Selected applications of Herrmann-Beller’s catalyst in organic synthesis.

 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 29

Some closely related analogues of 1, such as dimeric phosphapalladacycle

2-14 were also reported and applied in the Heck reactions (Table 2.2;
Fig. 2.2) (11,14,35). In 2008, Fu and Guo carried out a DFT study and pro-
posed two main pathways for the precatalyst activation. The computational
results indicated that the phosphapalladacycle 2 was activated via an olefin
insertion into a Pd-C bond followed by the β-hydride elimination, and sub-
sequent HBr abstraction under basic medium (Scheme 2.5) (36).

Scheme 2.5 Two possible mechanisms for the activation of palladacycle 2 in Heck
coupling.

Fig. 2.2 Examples of dimeric phosphapalladacycles.

 30
Palladacycles
Table 2.2 Dimeric Herrmann-Beller-type palladacycles in Heck reaction

Entry Palladacycle (mol% Pd) ArX R Solvent Time (h) Temp. (°C) Yield (%) Ref.
1 4 (2.0) p-MeOC6H4Br CO2n- DMA 44 138 74 11, 14
Bu
2a 4 (0.2) p-CHOC6H4Cl CO2n- DMA 24 130 40 11, 14
Bu
3 5 (2.0  104) p-MeC(O) CO2n- DMA 20 170 85 35
C6H4Br Bu
4 6 (2.0  102) p-MeC(O) CO2n- DMA 24 130 98 35
C6H4Br Bu
5 14 (10.0) C6H5Br CO2Me DMA 48 100 97 37
6 14 (0.4) o-CHOC6H4Br CO2Me DMA 10 100 99 37
7 15 (0.1) p-FC6H4Br Ph DMA 20 140 3 38
a
LiBr was added as an additive.
 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 31

Recoverable and hence reusable catalytic systems are attractive means for
cross-coupling reactions. Herrmann-Beller’s catalyst anchored on a
polystyrene-supported matrix 14 (37) or entrapped in zeolites NaY 15
(38) were prepared and examined as the possible catalysts for Heck and
Sonogashira reactions of aryl iodides and bromides. For the Herrmann-
Beller’s catalyst entrapped in the zeolites NaY, a very low activity was
obtained with only 3% GC yield. It is believed that the steric hindrance
of the complexes in the zeolite super cage limited the diffusion of the educts
and/or products and the accessibility of the metal center for the educts.
Multicomponent reactions are an attractive protocol for synthesizing
complex molecules. In 2012, the Malinakova group reported an investigation
of phosphapalladacycles 16–18 in the three-component coupling of aryl-
boronic acids, allenes and imines for accessing the homoallylic amines
(Scheme 2.6) (39). The P-heteroatom offers back-bonding via the
d-orbitals and diminished the electron density at the Pd(II) center in 1-bonded
allyl-Pd(II) intermediate and thus resulted in low product yield. Phos-
phapalladacycle 18 gave a very low catalytic activity when compared to the
traditional Pd(OAc)2/P(t-Bu)3 catalytic system. It is expected that the four-
membered cyclopalladated ligands formation should be facile.

Scheme 2.6 Three-components Heck reaction of arylboronic acids, allenes, and imines.

Monomeric form of Herrmann-Beller’s catalyst was also effective for the

Heck reaction (Table 2.3). The acetylacetonate palladacycles were prepared
and they showed excellent performance in the Heck coupling of aryl bro-
mides (40,41). Unfortunately, only 1%–2% product yield could be obtained
when chlorobenzene was used.
32 Palladacycles

Table 2.3 Monomeric-form Herrmann-Beller-type palladacycles in Heck reaction

Entry Palladacycle (mol% Pd) ArX Yield (%) Ref.

1 19 (0.35) C6H5I 83 40
2 20 (0.1) C6H5I 90 40
3 21 (1.0) C6H5Br 80 41
4 22 (1.0) C6H5Br 94 41
5 23 (1.0) C6H5Br 86 41
6 24 (1.0) C6H5Br 94 41
7 25 (1.0) C6H5Br 90 41
8 21 (0.1) MeC(O)C6H4Cl 51 41
9 22 (0.1) MeC(O)C6H4Cl 8 41
10 23 (0.1) MeC(O)C6H4Cl 50 41
11 24 (0.1) MeC(O)C6H4Cl 34 41
12 25 (0.1) MeC(O)C6H4Cl 38 41

N-Heterocyclic carbenes (NHC) are well-known electron-rich, neutral

σ-donor ligands in transition metal chemistry. By combining the features of
NHC into the phosphapalladacycle, an improved catalyst system was devel-
oped. The mono-carbene-substituted complex with various bulky group
attached 26-30 gave different effects to the catalyst efficacy in the Heck reac-
tion of activated aryl bromide/chloride with styrene (Scheme 2.7) (42).

2.1.2 Other Dimeric and Monomeric Phosphapalladacycles

Inspired by the initial groundwork of the Herrmann-Beller’s catalyst, sub-
sequent development of other related phosphapalladacycles for Heck cou-
pling reaction continues. Several monomeric and dimeric palladacycles
were designed and are depicted in Fig. 2.3.
Phosphapalladacycle 46 can be easily synthesized from 2-diphenylphosphino-
20 -methylbiphenyl (L1) by Pd-catalyzed reaction. It is designed as a “mixed
catalyst” in which it combines Herrmann’s framework with a sterically
demanding biphenyl moiety. The performance of 46 and the conventional
 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 33

Scheme 2.7 NHC-phosphapalladacycles with Herrmann’s catalyst skeleton in Heck

reaction.

biphenyl phosphine ligand L1 were compared in Heck coupling of different

substituted olefin. Catalyst 46 gave both terminal and internal products
when 1,1-disubtituted olefins were coupled with aryl bromides, yet L1 gave
terminal products as the main product (46) (Table 2.4, Entry 17).
In 2011, the Matano group reported examples of porphyrin-appended
phosphapalladacycles 40–43, and studied the effect of the central metals
on the catalytic activity in Heck reactions (Fig. 2.3, Table 2.4, Entries
11–14) (44). When the central metal was Ni, its catalytic activity was better
than the Zn- and the free-base-one. The results were found not to be simply
correlated with the σ-donating ability of the P-donor and the electron-
richness of the porphyrin π-systems.
A water-soluble palladacycle aqua complex 51 was designed for the Heck
coupling of benzoic acid derivatives in water (Scheme 2.8) (48,49). The reac-
tion was found to be highly dependent on the pH environment. When the pH
value was larger than 11.5, a decrease in the catalytic reactivity was observed
due to the deprotonation of the H2O ligand on 51. The reaction also pro-
ceeded smoothly when aryl bromides were used (51% for Br, 70% for I).
Kwong and co-workers developed an indolyl-phosphine ligand CM-
phos for cross-coupling reactions. The palladium complex derived from
CM-phos and Pd(OAc)2 was found in a dimeric form with two acetate
34 Palladacycles

Fig. 2.3 Examples of phosphapalladacycles.

Table 2.4 Other phosphapalladacycles in Heck reaction

Entry Palladacycle (mol% Pd) ArX R Solvent Time (h) Temp. (°C) Yield (%) Ref.

Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions

1 31 (0.1) C6H5Br Ph DMA 19 130 79 41
2 32 (0.2) p-MeC(O)C6H4Br CO2n-Bu DMA 13 140 100 43
3 33 (0.1) C6H5Br Ph DMF 30 115 77 40
4 34 (0.5) C6H5I Ph DMF 24 95 56 40
5 35 (0.26) p-MeC(O)C6H4Br Ph DMF 7 125 94 40
6 35 (0.26) p-CNC6H4Br Ph DMF 7 125 85 40
7a 38 (0.2) p-MeOC6H4Br Ph DMA 18 130 85 41
8 38 (0.2) p-MeC(O)C6H4Cl Ph DMA 14 130 29 41
9 39 (1.0  104) p-MeC(O)C6H4Br CO2n-Bu DMA 6 180 100 43
10 39 (1.0) C6H5Cl Ph TBAB 17 150 45 16
11 40 (0.1) p-CHOC6H4Br CO2n-Bu DMA 7 135 100 44
12 41 (0.1) p-CHOC6H4Br CO2n-Bu DMA 8 135 <20 44
13 42 (0.1) p-CHOC6H4Br CO2n-Bu DMA 8 135 <20 44
14 43 (0.1) p-CHOC6H4Br CO2n-Bu DMA 9 135 93 44
15 44 (1.0) C6H5Cl Ph DMF 4 130 52 45
16 44 (1.0) p-NO2C6H4Cl Ph DMF 4 130 95 45
17 46 (0.2) C6H5Br Ph DMA 1 130 60 46
18 47 (1.0  10–2) C6H5Br Ph DMF 10 140 89 47
19 48 (0.1) C6H5Br Ph DMF 5 140 89 47
20 49 (0.1) C6H5Br Ph DMF 5 140 92 47
21 50 (0.1) C6H5Br Ph DMF 5 140 63 47
a
TBAB was added as an additive.

35
36 Palladacycles

Scheme 2.8 Water-soluble phosphapalladacycle 51 in Heck reaction.

bridging groups (Fig. 2.4) (50). The six-membered cyclometallated ring is

puckered and it was employed in various cross-coupling reactions with
excellent catalytic efficacy.
C56 C15
C57 C14
C55 C16 C17
C13
C58 N1
C54 C11
C53 C2 C12
C5
C37
02 C10 C9 C6
C47 P2 C36
C51 C52
C1 C4
C32 01 C7
Pd1 C3 C22
C18 C21
C49 Pd2 C33 C35
C50 C48
C34 P1 C8 C23 C20
04
C39 C19
03
C38 C30
C40 C24
C29
N2 C25
C41 C31
C46
C45 C28 C26
C42
C27
C43 C44

Fig. 2.4 Indolyl-phosphine palladacycle 52 derived from CM-phos.

2.1.3 Diphosphine-Palladacycles
Chelating bisphosphine-Pd-dihalide complexes are good catalysts for Heck
reaction. Different diphosphine-containing palladacycles were developed
(Fig. 2.5; Table 2.5) (51). Phosphapalladacycle 56–59 were designed with dif-
ferent length of the carbon chain between the P-donor (52). Interestingly, the
longer the carbon chain, the lower the reactivity of the catalyst in the Heck
reaction. For the diphosphine palladacycle 61–62, the Heck coupling of aryl
halides and ethyl acrylate underwent smoothly with NMP and Cs2CO3 (53).
When styrene was used in place of ethyl acrylate, DMF and K2CO3 were nec-
essary to promote this reaction. Mono-ylide phosphine palladacycle 63, 64,
and 71 were also successful precatalysts for Heck reaction of aryl bromides and
chlorides (56,57). The chelation of ylide through the ylidic carbon atom and
phosphino group afforded six-membered ring where the P,C coordination
was confirmed by the single crystal X-ray crystallography. The Sabounchei
group further reported a bis-ylide palladacycle in comparing the catalytic
activity of its mono-ylide form in Heck coupling (54).
 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 37

Fig. 2.5 Examples of diphosphine-palladacycles.

2.2 Sonogashira Cross-Coupling Reaction

Nowadays, the mostly employed reaction conditions for the Sonogashira
coupling still involve simple phosphine-based palladium complexes such
as [Pd(PPh3)2Cl2], [Pd(PPh3)4], [Pd(dppe)Cl2], [Pd(dppp)Cl2], and [Pd
(dppf )Cl2] as the catalysts, (58) in which a catalytic amount of copper(I) salt
is required (59). Excellent product yields were often obtained by using these
phosphine-based palladium complexes, under a medium of excess amine (or
inorganic base). High catalyst and co-catalyst loadings are required in more
demanding situations as in the case of nonactivated aryl chlorides. Consid-
ering the drawback of high-cost palladium catalysts in these C2sp-Csp cross-
coupling reactions, (60) the search for new phosphine-types of ligands
amendable to improve the catalytic efficiency is necessary.
Herrmann-Beller’s catalyst 1 served as the landmark catalyst for most of
the cross-coupling reactions. In 1996, Herrmann demonstrated the Sonoga-
shira coupling which proceeded well with a wide range of aryl bromides
(61). Later investigation showed that even without the addition of CuI,
aryl bromides could also be coupled smoothly with phenylacetylene to
give the desired product. However, when aryl chlorides were used as
the electrophilic partner, no satisfactory results were obtained. It was syn-
thetically notable that the tolane products synthesized by Sonogashira
coupling could be further coupled with 2-bromobenzaldehyde to afford
2,3-diphenylindenone (62).
Table 2.5 Diphosphine palladacycles in Heck reaction

38
Palladacycle (mol% Time Temp. Yield

Palladacycles
Entry Pd) ArX R Solvent Base (h) (°C) (%) Ref.
1 53 (3.3  103) 4-MeC(O) Ph DMF TBA 66 125 91 52
C6H4Br
2 55 (0.23) 4-CNC6H4Br Ph DMF TBA 12 125 75 52
3 56 (5.8  102) 4-MeC(O) Ph DMF TBA 24 125 88 52
C6H4Br
4 57 (6.0  102) 4-MeC(O) Ph DMF TBA 24 125 87 52
C6H4Br
5 58 0.465 4-MeC(O) Ph DMF TBA 24 125 75 52
C6H4Br
6 59 (1.5  102) 4-MeC(O) Ph DMF TBA 24 125 79 52
C6H4Br
7 60 (5.2  102) 4-MeC(O) Ph DMF KHCO3 24 125 82 52
C6H4Br
8 61 (1.0  103) C6H5Cl Ph DMF K2CO3 4 130 77 53
9 62 (1.0  103) C6H5Cl Ph DMF K2CO3 4 130 69 53
10 64 (1.0  103) C6H5Cl CO2Et NMP K2CO3 24 130 71 54
11 65 (1.0  103) 4-MeOC6H4Br Ph dioxane K2CO3 16 80 75 55
12 66 (1.0  103) 4-MeOC6H4Br Ph dioxane K2CO3 16 80 70 55
13 67 (1.0  103) 4-MeOC6H4Br Ph dioxane K2CO3 16 80 84 55
14 68 (1.0  103) 4-MeOC6H4Br Ph dioxane K2CO3 16 80 68 55
15 63 (1.0  103) C6H5Cl CO2Et DMF K2CO3 24 180 74 56
16 69 (1.0  103) 4-MeOC6H4Br Ph dioxane K2CO3 16 80 80 55
17 70 (1.0  103) C6H5Cl CO2Et NMP K2CO3 24 130 76 54
18 71 (1.0) C6H5Cl Ph DMF/ K2CO3 6 reflux 76 57
H2 O
 Palladacycles as Precatalysts for Heck and Sonogashira Cross-Coupling Reactions 39

The polymer-supported diphenylphosphinoethane palladium(0) com-

plex 72 was recently reported and used as the precatalyst in the copper-free
Sonogashira coupling of aryl iodides with terminal alkynes (Scheme 2.9)
(63). Excellent product yields (85%–98%) resulted even at room tempera-
ture conditions. This catalyst could be recycled and reused up to five times
without considerable loss of activity.

Scheme 2.9 Sonogashira reaction catalyzed by a polymer-supported Pd(0)

diphenylphosphinoethane complex.

Tamami and Ghasemi reported the immobilization of Pd(0) NPs into a

modified cross-linked polyacrylamide containing phosphinite 73 (64). The
catalytic performance of 73 was studied in the Sonogashira reaction of various
aryl iodides (80%–90%), bromides (75%–87%), and chlorides (70%–78%)
as illustrated in Scheme 2.10. According to ICP analysis, 4.8% leaching of pal-
ladium was observed during the reaction with iodobenzene, yet without sig-
nificant loss of activity after five runs.

Scheme 2.10 Sonogashira coupling reaction catalyzed by a crosslinked polyacrylamide

containing phosphinite complex.

In addition to the general mechanism of copper-free Sonogashira reac-

tion, a mechanism particularly referring to the catalyst 72 was proposed
(Fig. 2.6). The catalytic cycle is initiated, as usual, by the oxidative addition
of the aryl halide in step 2. Subsequent insertion of the carbon-carbon triple
bond to Ar-Pd-X generates the alkenylpalladium species (step 3), which
then undergoes β-hydride elimination (step 4) to afford the disubstituted
alkyne. Finally, Pd(0) is regenerated by reductive elimination of the
Pd(II) compound in the presence of a base in step 5.
Another Random Scribd Document
with Unrelated Content
It was our first dinner, and dressed by our new cook, Munseer Cordongblew. I bore it very well, eating,
for my share, a filly dysol allamater dotell, a cutlet soubeast, a pully bashymall, and other French
dishes: and, for the frisky sweet wine, with tin tops to the bottles, called Champang, I must say that me
and Mrs. Coxe-Tuggeridge-Coxe drank a very good share of it (but the Claret and Jonnysberger, being
sour, we did not much relish); however, the feed, as I say, went off very well, Lady Blanch Bluenose
sitting next to me, and being so good as to put me down for six copies of all her poems; the Count and
Baron Von Punter engaging Jemimarann for several waltzes, and the Field-Marshal plying my dear
Jemmy with Champang until, bless her! her dear nose became as red as her new crimson satin gown,
which, with a blue turban and Bird-of-Paradise feathers, made her look like an Empress, I warrant.
Well, dinner past, Mrs. C. and the ladies went off:—thunder-under-under came the knocks at the door;
squeedle-eedle-eedle, Mr. Wippert's fiddlers began to strike up; and, about half-past eleven, me and the
gents thought it high time to make our appearance. I felt a little squeamish at the thought of meeting a
couple of hundred great people; but Count Mace, and Sir Gorman O'Gallagher taking each an arm, we
reached, at last, the drawing-room.
The young ones in company were dancing, and the Duchess and the great ladies were all seated,
talking to themselves very stately, and working away at the ices and macaroons. I looked out for my
pretty Jemimarann amongst the dancers, and saw her tearing round the room along with Baron Punter,
in what they call a gallypard; then I peeped into the circle of the Duchesses, where, in course, I
expected to find Mrs. C.; but she wasn't there! She was seated at the farther end of the room, looking
very sulky; and I went up, and took her arm, and brought her down to the place where the Duchesses
were. "O, not there!" said Jemmy, trying to break away. "Nonsense, my dear," says I, "you are Missis,
and this is your place:"—then, going up to her Ladyship the Duchess, says I, "Me and my Missis are
most proud of the honour of seeing of you."
The Duchess (a tall red-haired grenadier of a woman) did not speak.
I went on. "The young ones are all at it, ma'am, you see: and so we thought we would come and sit
down among the old ones. You and I, ma'am, I think, are too stiff to dance."
"Sir?" says her Grace.
"Ma'am," says I, "don't you know me? my name's Cox—nobody's introduced me; but, dash it, it's my
own house, and I may present myself—so give us your hand, ma'am."
And I shook hers in the kindest way in the world: but, would you believe it? the old cat screamed as if
my hand had been a hot 'tater. "Fitzurse! Fitzurse!" shouted she; "help! help!" Up scuffled all the other
Dowagers—in rushed the dancers. "Mamma! mamma!" squeaked Lady Julia North Pole. "Lead me to my
mother," howled Lady Aurorer; and both came up and flung themselves into her arms. "Wawt's the
raw?" said Lord Fitzurse, sauntering up quite stately.
"Protect me from the insults of this man," says her Grace. "Where's Tufthunt? he promised that not a
soul in this house should speak to me."
"My dear Duchess," said Tufthunt, very meek.
"Don't Duchess me, sir. Did you not promise they should not speak; and hasn't that horrid tipsy wretch
offered to embrace me? Didn't his monstrous wife sicken me with her odious familiarities? Call my
people, Tufthunt! Follow me, my children!"
"And my carriage; and mine, and mine!" shouted twenty more voices; and down they all trooped to the
hall: Lady Blanch Bluenose, and Lady Max among the very first; leaving only the Field-Marshal, and one
or two men, who roared with laughter ready to split.
"O, Sam," said my wife, sobbing, "why would you take me back to them? they had sent me away
before! I only asked the Duchess whether she didn't like rum-shrub better than all your Maxarinos and
Curasosos: and, would you believe it? all the company burst out laughing; and the Duchess told me just
to keep off, and not speak till I was spoken to. Imperence! I'd like to tear her eyes out."
And so I lo believe my dearest Jemmy would!
 TOM THE DEVIL.
A FRAGMENT OF THE BIOGRAPHY OF 1839.
"I do declare, upon an affidavit,
Romance I've never read like that I've seen:
Nor, if unto the world I ever gave it,
Would some believe that such a tale had been!"—Byron.

It was a little past the noon of a lovely day in the last Autumn, that, as I rode towards the Doncaster
race-course, to enjoy an hour of its rural revelries, before the serious business of the Leger commenced,
I found myself hailed by a voice, and an arm of a red silk robe de chambre, from a drawing-room
window of the "Salutation." Now, when we set out in prepense search of adventure, it don't require the
song of the Syrens to induce us to luff up to a hail. Turning under the gateway, therefore, I dismounted,
and taking my way upstairs, made the apartment for which I was bound, with but little difficulty. The
chamber was, certainly, not the worst specimen I had ever seen of the unfortunate world whereof it
formed an item. The appointments combined no ordinary degree of comfort and elegance, while a
table, placed at one of the windows, was stocked after a manner that would have done honour to the
corporation of Bristol. Among various plats, consisting of cold partridges, French patés, devil'd grouse,
and varieties of choice fruit, arose the graceful forms of tapering flasks, eloquent of many a rare and
precious vintage. The lord or all, arrayed in a robe of scarlet silk, lined with purple of a like material, lay,
dishevelled, in Sybarite indulgence, upon a sofa adjoining this teeming board. "Couchant," I knew him
not; but as he rose to receive me, there, in that silk attire, stood confessed the worthy, a fragment of
whose biography I am now in the act of perpetuating—the veritable hero of these presents, even Tom
the Devil himself. As my acquaintance with him at the time (and indeed in all subsequent experience)
was of a very desultory character, this introduction of him to the reader must be of a similar nature.
Ireland was the land of his birth; but the particulars of his parentage were less definitely ascertained. I
was assured he had an uncle (from an episode in his life that it is not convenient here to enter upon),
and, indeed, he himself admitted that he was in the habit of frequent intercourse with a person
distinguished by that appellation. However, for our present purpose, it is enough that he was an
eccentric, endowed with little of the tedious coherence of the merely common-place. When we laugh at
the samples of his compatriots, put before us by the playwright and the actor, we regard them as
pleasant burlesques, cleverly, though unnaturally, got up. Reader! if haply thou hast had no personal
experience of Erin as it is, permit me to offer thee this characteristic fragment.
"Ould fellow," said the fiend, clutching my hand in a monstrous horny fist, "by my sowl, I'm grately
plazed to meet ye in these parts: when did ye come to Doncaster? and where do ye hang out? and how
long do ye stop?" "Came by the Edinburgh mail yesterday morning; at my old lodgings at the saddler's,
nearly opposite the Rooms: leave for town to-morrow," said I. "That's a nate way of doing business,
sure enough," was the commentary; "ounly I can't larn the sinse of going to a private lodging, where, if
you ordher a kidney for breakfast, you're expected to fork out to the butcher. See how I carry on the
war, and never hard the ghost of an inquiry about coin sense I sot fut in the house. A hotel's the place
for me! I've thried 'em all, from the Club-house at Kilkinny to the Clarendon, and, by the holy poker,
never wish mysilf worse luck than such cantonments! Arrah! what more does a man require than a
place where, if he wants a bottle of claret, all he has to do is to ring the bell for it? Dine with me to-
night," continued the social economist; "they put you to trough very respectably in this same shop: ask,
and have, that's the ticket." I declined, with thanks; urging a previous engagement, and made a
demonstration of leave-taking.—"Fill a bumper of sparkling burgundy before you go, any how," said my
hospitable host; "you'll find it a gentlemanly morning tipple! if this be war, may we never have pace;
here's to our next merry meeting, and may we never know the want of oceans of wine, plantations of
tobacco, cart-loads of pipes, lots of purty girls, and a large room to swear in.—Farewell."
About a fortnight after the date to which the foregoing refers, chance placed me in Dublin, and the
coffee-room of Morisson's hotel, towards eight, P.M., with the remnant of a bottle of Sneyd and Barton's
"twenty-two" before me. With his back to one of the fires stood what had all the outward appearance of
a scare-crow—a figure made up of a coat that no respectable old clothesman would degrade his bag
withal, and a superlatively "shocking bad hat." The waiters were eyeing it in a most suspicious manner,
and I was wondering why they didn't kick it into the street, when, to my utter amazement, the "horrible
illusion" stalked towards the place where I sat, and, in accents familiar to my ear, wheezed out, "Ould
fellow, by my sowl I'm grately plazed to meet ye in these parts!" There could be no mistake about it—
Tom, it was—"sed quanto mutatus ab illo diabolo." "A chair," said I, to a waiter who was now staring at
us both, like the Trojan who drew Priam's curtain—"bring a chair and another wine-glass;" and pouring
a bumper, I pushed it towards my vis-à-vis. "Drink, Tom," I continued; "whatever maybe your object in
this masquerading, a drain of Bordeaux will never hurt you: drink, and then, unless it's treason, leave
off your damnable faces and begin." "Masquerading!" exclaimed the scurvy libel upon the Doncaster
Sardanapalus, with a smile as much out of character on such a face as a rose in an undertaker's button-
hole; "by the piper of Blessingtown, it's rale arnest! Unless the smell of mate be disagreeable to you
after dinner, for the honour of dacency tell them to get me a few steakes without delay: I'm as full of
wind as a blown blather: like my ould coat, I'm dying of the stitches." Several handsome sections of a
sirloin having been disposed of, without the ceremony of oyster sauce, and a wish for materials for
punch (expressed with a look of intense yearning), duly administered to, "the Devil" thus detailed his
progress since our parting:—
"It's mighty nice for philosophers, on three courses and a dessert, to talk about the uses of adversity
being sweet; but if they'll thry a genuine sample of it, say a can of poorhouse soup (biling dish-wather,
flavoured with a farthing rushlight to the gallon), perhaps they would alther their opinions a leetle.
However, there's no need for these reflections now. How did the Leger serve you?—I lost (that was of
very little consequence)—but I didn't win, and that was, as I was entirely without funds just thin. Well, I
wint to ould——'s, at night (having transmogrified what odd togs I could muster into cash, by the
assistance of my father's brother), and if it had been 'vingt un,' or 'loo,' we were playing, my fortune
would have been made, for I got aces by the baker's dozen. But at hazard they're not the thing: so I
was turned inside out as clane as a pudden-bag—indeed rather claner, as they got out of me about four
times as much as ever I contained. Whin I rose to lave the house (who was to stay there with such a
run against him?), the blaggards objected to my taking my Macintosh and hat with me, bad luck to
them! and so I had to return home as classically undressed as William the Third in College Green. A
man without hat or coat, however, isn't so well thought of now-a-days as among the ancient Romans;
and, as misfortunes never come alone, without half a score to keep them company, I found my credit at
the hotel had gone to look after that which I left at ould——'s hazard-table. No gentleman should ever
demane himself by running the risk of a notice to quit; so, instead of stopping at the race-ground next
morning, I walked quietly on to Newark. It's raly a purty walk from Doncaster to Liverpool—that is to
say, for those who are fond of pedesthrian exercise—I like riding better; and so I wasn't sorry whin I
seen the Mersey rowling away on my right. Having left my body-coat in pledge for the last night's
lodging, I had to borry one that was hanging on a stick in a pay-field, and as my shoes had given in at
Norman Cross, I was not just the cut for a fashionable hotel. A bit of an ague I was lucky enough to
pick up at Grantham, however, qualified me for a berth in the hospital, where I remained till I was
convalescent—which manes on the brink of the grave; so I left, to save them the trouble of burying me.
There's no stepping from the pier-head at Liverpool to the North Wall here, so that there was nothing
left for it but an application, in form of a distriss'd Irish agriculturist, to the export committee, and they
furnished me with a pass for the hould of a steamer, and a fourpenny loaf for sea-store. If our passage
hadn't been a bad one, I should have done well enough; but my provision was out before we reached
the Orme's Head, and I was ready to ate my brogues whin I caught sight of you. Never mind! worse
luck now—better another time; as Shakspeare says—'Life's a stage, and every man plays many parts.'
Anthony to-day, Scrub to-morrow."
THE DUST ABOUT THE GOLD DUST.
A lac of lost rupees might make
The loser cry, "alack!"
But think upon their grief who're robb'd
Of gold, and by the sack!
And what a dust they did kick up
To get their gold dust back!

To rob two British merchants thus

Did wicked Jews combine;
They knew that gold dust had arriv'd,
And what house did consign:
Said each, "Since from the mine it comes,
I'll make some of it mine!"

With firm right-hand a bad Clerk forg'd

The write-hand of the Firm:
The Customs gave the box (where was
Reflection, then, O Sturm!)
And all the bags of gold, inside,
Were bagg'd, like briefs in Term.

They cabb'd the booty all away,

That boots might leave no tracks;
Then lugg'd the sacks out, one by one,
And laid them on their backs:
And marshall'd them all in a row,
Like troops of Marshal Saxe!

They hid them in the pot-house low

Of Moses—"fence," and "do;"
For wealth amass'd, 'tis doubtful how,
Call'd "Money Moses," too;
The world gave him that Christian name,
Because he was a Jew!

Now Moses had a daughter, dark,

A damsel all discreet,
He gave the gold into her hands,
And she perform'd the feat
Of selling it to a goldsmith Jew,
Another wicked cheat!

Into the goldsmith's crucible

The bag of ore she thrust;
Then, as the dust dissolv'd, she cried,
"Come, down, now, with your dust!"
And he, all in the melting mood,
Said, "I suppose I must."

At once some pounds for every ounce

He paid upon the spot;
A shining ingot soon was turn'd
Out of the melting-pot.
A precious scrape the Jew got in,
All through that same ingot.
For 'mong the thieves divisions rose,
Like vinegar with oil,
They disagreed—for one would still
The other rob and foil:
And all their deep-laid schemes were spoil'd
In sharing out the spoil.

At last, of their dissentient rows,

A 'peach became the fruit,
One Jew, in jew-rious, blabb'd about
The dust and the dispute:
The gang were taken, and the law
Fell cute to prosecute.

Then Moses, goldsmith, damsel, clerk,

Into their pickle fell;
They found they were no sooner sold
Than clapp'd into a cell:
From which not one of them could bolt,
While bolted in so well!

At last the trial did come on,

The Court was in a throng,
The Evidence against them all
Was heavy, dense, and strong;
Guilty the Ju-ry found the Jews,
And so might end my song:—

But no; the lawyers found a flaw,

To keep the law at bay—
Not Bot'ny-bay—the way by which
They should be sent away—
So one or two, by getting off,
May still in London stay.

Now all the Culprits' fates depend

On what the Judges choose;
To sin-a-gain, not Synagogue,
Their liberty they'd use:
So England hopes her Judges wont
Emancipate the Jews!

MARCH. [1840.
 MARCH DUST.—THE BELL SAVAGE.
That dustman's bell—that dustman's bell— SEASON'S SIGNS.
What horrid tales its tongue did tell! ———————
He surely served his country well ♈♂♒
Who freed us from the dustman's bell. 'Tis hard for
dust
When basking in the morning beams, they may not
I revell'd in Elysian dreams, ring;
'Mong flowers, by Helicon's sweet bubble,
♀♐♄⊕
Inventing rhymes with little trouble;
because,
What did so soon the charm dispel,
in March, 'twill
As that detested dustman's bell!
buy
Or, thinking all the night away, a King.
On debts ungather'd, bills to pay;
And pondering how it might be known
Whether 'twas best to hang or drown,
I've dropped into a wearied snooze,
And quickly tied the fatal nooze,
Then, starting at my funeral knell,
Found 'twas the dustman's passing bell.

When dining with a chosen few,

"The jolly cocks," a noble crew,
I've wander'd home supremely glorious,
And even dared to be uproarious,
The champagne mounting in my head,
Not knowing how I got to bed;
And, waking with the dawn, I've found
The room and bed-post turning round; A Jolly Cock
What time, in accents loud and clear,
My loving, lawful, lady dear,
With curtain'd privilege elate,
And heedless of my fallen state,
The round of all my faults doth tell;
Spite of my headache and my woes,
Exhausted, I begin to doze,
And dream I hear the dustman's bell,

That dustman's bell—that dustman's bell, &c.

15. Animal Magnetism Exhibitions stopped at the North London Hospital. A Dustman and his
Belle.
The cunning patient, we are told,
Would only move when touch'd by gold.
That would not suit the learned elves;
The Doctors wanted it themselves.

25. Gold-dust robbery. New version of "The Golden Fleece."

MARCH.—A day with the Surrey Hounds
 MARCH.—A Day with the Surrey Hounds.
Our ball had failed so completely, that Jemmy, who was bent still upon fashion, caught eagerly at
Tagrag's suggestion, and went down to Tuggeridgeville. If we had a difficulty to find friends in town,
here there was none; for the whole county came about us, ate our dinners and suppers, danced at our
balls—ay, and spoke to us too. We were great people, in fact; I a regular country gentleman; and, as
such, Jemmy insisted that I should be a sportsman, and join the county hunt. "But," says I, "my love, I
can't ride." "Pooh! Mr. C.," she said, "you're always making difficulties; you thought you couldn't dance a
quadrille; you thought you couldn't dine at seven o'clock; you thought you couldn't lie in bed after six;
and haven't you done every one of these things? You must and you shall ride!" And when my Jemmy
said "must and shall," I knew very well there was nothing for it: so I sent down fifty guineas to the
hunt, and, out of compliment to me, the very next week I received notice that the meet of the hounds
would take place at Squashtail Common, just outside of my lodge-gates.
I didn't know what a meet was; and me and Mrs. C. agreed that it was most probable the dogs were to
be fed there: however, Tagrag explained this matter to us, and very kindly promised to sell me a horse,
a delightful animal of his own; which, being desperately pressed for money, he would let me have for a
hundred guineas, he himself having given a hundred and fifty for it.
Well, the Thursday came; the hounds met on Squashtail Common; Mrs. C. turned out in her barouche
to see us throw off; and being helped up on my chestnut horse, Trumpeter, by Tagrag and my head
groom, I came presently round to join them.
Tag mounted his own horse; and as we walked down the avenue, "I thought," he said, "you told me
you knew how to ride; and that you had ridden once fifty miles on a stretch!"
"And so I did," says I: "to Cambridge, and on the box too."
"On the box?" says he; "but did you ever mount a horse before?"
"Never," says I, "but I find it mighty easy."
"Well," says he, "you're mighty bold for a barber; and I like you, Coxe, for your spirit;" and so we came
out of the gate.
As for describing the hunt, I own, fairly, I can't. I've been at a hunt, but what a hunt is—why the horses
will go among the dogs and ride them down—why the men cry out "yooooic"—why the dogs go
snuffling about in threes and fours, and the huntsman says, "Good Towler—good Betsy;" and we all of
us after him, say, "Good Towler—good Betsy" in course: then, after hearing a yelp here, and a howl
there, tow, row, yow, yow, yow! bursts out, all of a sudden, from three or four of them, and the chap in
the velvet cap screeches out (with a number of oaths I shan't repeat here), "Hark, to Ringwood!" and
then, "There he goes!" says some one; and all of a sudden, helter skelter, skurry hurry, slap bang,
hooping, screeching, and hurraing, blue coats and red coats, bays and greys, horses, dogs, donkeys,
butchers, baronets, dustmen, and blackguard boys, go tearing, all together, over the common after two
or three of the pack that yowl the loudest. Why all this is, I can't say, but it all took place the second
Thursday of last March, in my presence.
Up to this I'd kept my seat as well as the best, for we'd only been trotting gently about the field until
the dogs found: and I managed to stick on very well; but directly the tow-rowing began, off went
Trumpeter like a thunderbolt, and I found myself playing among the dogs like the donkey among the
chickens. "Back, Mr. Coxe," holloas the huntsman; and so I pulled very hard, and cried out, Wo! but he
wouldn't; and on I went galloping for the dear life. How I kept on is a wonder; but I squeezed my knees
in very tight, and shoved my feet very hard into the stirrups, and kept stiff hold of the scruff of
Trumpeter's neck, and looked betwixt his ears as well as ever I could, and trusted to luck, for I was in a
mortal fright, sure enough, as many a better man would be in such a case, let alone a poor hairdresser.
As for the hounds, after my first riding in among them, I tell you, honestly, I never saw so much as the
tip of one of their tails; nothing in this world did I see except Trumpeter's dun-coloured mane, and that
I gripped firm: riding, by the blessing of luck, safe through the walking, the trotting, the galloping, and
never so much as getting a tumble.
There was a chap at Croydon, very well known as the "Spicy Dustman," who, when he could get no
horse to ride to the hounds, turned regularly out on his donkey; and on this occasion made one of us.
He generally managed to keep up with the dogs, by trotting quietly through the cross roads, and
knowing the country well. Well, having a good guess where the hounds would find, and the line that sly
Reynolds (as they call the fox) would take, the Spicy Dustman turned his animal down the lane, from
Squashtail to Cutshins Common, across which, sure enough, came the whole hunt. There's a small
hedge and a remarkably fine ditch here; some of the leading chaps took both, in gallant style; others
went round by a gate, and so would I, only I couldn't; for Trumpeter would have the hedge, and be-
hanged to him, and went right for it.
Hoop! if ever you did try a leap! Out go your legs, out fling your arms, off goes your hat; and the next
thing you feel, that is, I did, is a most tremendous thwack across the chest, and my feet jerked out of
the stirrups; me left in the branches of a tree; Trumpeter gone clean from under me, and walloping and
floundering in the ditch underneath. One of the stirrup-leathers had caught in a stake, and the horse
couldn't get away; and neither of us, I thought, ever would have got away; but, all of sudden, who
should come up the lane but the Spicy Dustman!
"Holloa!" says I, "you gent, just let us down from this here tree!"
"Lor!" says he, "I'm blest if I didn't take you for a robin."
"Let's down," says I; but he was all this time employed in disengaging Trumpeter, whom he got out of
the ditch, trembling and as quiet as possible. "Let's down," says I. "Presently," says he; and taking off
his coat, he begins whistling and swishing down Trumpeter's sides and saddle; and, when he had
finished, what do you think the rascal did?—he just quietly mounted on Trumpeter's back, and shouts
out, "Git down yourself, old Bears-grease; you've only to drop! I'll give your oss a hairing arter them
'ounds; and you, vy you may ride back my pony to Tuggeridgeweal!" And with this, I'm blest if he didn't
ride away, leaving me holding, as for the dear life, and expecting every minute the branch would break.
It did break too, and down I came into the slush; and when I got out of it, I can tell you I didn't look
much like the Venuses or the Apollor Belvidearis what I used to dress and titivate up for my shop-
window, when I was in the hairdressing line, or smell quite so elegant as our rose-oil. Faugh! what a
figure I was!
I had nothing for it but to mount the dustman's donkey (which was very quietly cropping grass in the
hedge), and to make my way home; and after a weary, weary journey, I arrived at my own gate.
A whole party was assembled there. Tagrag, who had come back; their Excellencies Mace and Punter,
who were on a visit; and a number of horses walking up and down before the whole of the gentlemen
of the hunt, who had come in after losing their fox! "Here's Squire Coxe!" shouted the grooms. Out
rushed the servants, out poured the gents of the hunt, and on trotted poor me, digging into the donkey,
and everybody dying with laughter at me.
Just as I got up to the door, a horse came galloping up, and passed me; a man jumped down, and
taking off a fantail-hat, came up, very gravely, to help me down.
"Squire," says he, "how came you by that there hanimal? Jist git down, will you, and give it to its
howner."
"Rascal!" says I, "didn't you ride off on my horse?"
"Was there ever sich ingratitude?" says the Spicy. "I found this year oss in a pond, I saves him from
drowning, I brings him back to his master, and he calls me a rascal!"
The grooms, the gents, the ladies in the balcony, my own servants, all set up a roar at this; and so
would I, only I was so deucedly ashamed as not to be able to laugh just then.
And so my first day's hunting ended. Tagrag and the rest declared I showed great pluck, and want me
to try again; but "no," says I, "I have been."

APRIL.—The finishing touch

1840.] APRIL.
 CAUGHT AT CATCHING.
To angle o' April! Shame and wicked deed, WEATHER.
Debarr'd, like March, from Anglo-Saxon lad; The
Nor May net profit must the fisher heed, Weather-Prophet,
For bad it is, and so it is for-bad! foiled,
doth loudly
In these—the fence months—'tis offence: for men vow,
To fish among the spawn were cruel sign:
John Bull should leave his Hook, and fishers then
Should be employed in quite another line.

'Twere graceless sure to fright the little fry

From family peace:—the Mayor, their quiet heeding
The die has cast that then they should not die,
Besides 'twould plainly be against good breeding!

The Thames is the Mayor's nest—a bitter dish

His Lordship gives its spoilers—name of fear;
Why 'tis admitted, even by the fish,
Diet of Worms was never more severe!

He tackles all the fishers: rightly deems Gentle Sport.

The sink of nets a sink of sin!—for boat, though
To ply the angler, wherry wicked seems; wrong before,
He will not have a single float afloat! I'm sure I've
hit it now;
In March, upon the Thames, march no man must;
April must heed his reign—Invade the spot,
And out of water he'll kick up a dust;
The year says May,—but he says you may not.

Woe to the mortal who shall founder there!

Let man shun Mansion House, and Lord Mayor's search;
He, like an eagle, sits, with savage stare,
Defying all the world to touch—his perch!

MORAL.

Fishers! forego your line for three months' length,

And fence, don't fish, in fence months now; for mind,
Tho' every week the Mayor put out his strength,
If there you are not found you are not fined!
Taking to their Eels. "The Bailiffs are coming, Oh dear! oh dear!"
 APRIL.—The Finishing Touch.
I was always fond of billiards: and in former days, at Grogram's, in Greek Street, where a few jolly lads
of my acquaintance used to meet twice a week for a game, and a snug pipe and beer, I was generally
voted the first man of the club; and could take five from John the marker himself. I had a genius, in
fact, for the game; and now that I was placed in that station of life where I could cultivate my talents, I
gave them full play, and improved amazingly. I do say that I think myself as good a hand as any chap in
England.
The Count, and his Excellency Baron von Punter, were, I can tell you, astonished by the smartness of
my play; the first two or three rubbers Punter beat me, but when I came to know his game, I used to
knock him all to sticks; or, at least, win six games to his four: and such was the betting upon me: his
Excellency losing large sums to the Count, who knew what play was, and used to back me. I did not
play except for shillings, so my skill was of no great service to me.
One day I entered the billiard-room when these three gentlemen were high in words. "The thing shall
not be done," I heard Captain Tagrag say. "I won't stand it."
"Vat, begause you would have de bird all to yourzelf, hey?" said the Baron.
"You sall not have a single fezare of him, begar," said the Count. "Ve vill blow you, M. de Taguerague;
parole d'honneur, ve vill."
"What's all this, gents," says I, stepping in, "about birds and feathers?"
"Oh," says Tagrag, "we were talking about—about—pigeon-shooting. The Count, here, says he will blow
a bird all to pieces at twenty yards, and I said I wouldn't stand it, because it was regular murder."
"Oh, yase, it was bidgeon-shooting," cries the Baron: "and I know no better sport. Have you been
bidgeon-shooting, my dear Squire? De fon is gabidal." "No doubt," says I, "for the shooters, but mighty
bad sport for the pigeon;" and this joke set them all a laughing ready to die. I didn't know then what a
good joke it was, neither; but I gave Master Baron that day a precious good beating, and walked off
with no less than fifteen shillings of his money.
As a sporting man, and a man of fashion, I need not say that I took in the "Flare-up," regularly; ay, and
wrote one or two trifles in that celebrated publication (one of my papers, which Tagrag subscribed for
me, Philo-pestitiæamicus, on the proper sauce for teal and widgeon; and the other, signed Scru-tatos,
on the best means of cultivating the kidney species of that vegetable, made no small noise at the time,
and got me in the paper a compliment from the editor). I was a constant reader of the Notices to
Correspondents, and my early education having been rayther neglected (for I was taken from my
studies and set, as is the custom in our trade, to practise on a sheep's-head at the tender age of nine
years, before I was allowed to venture on the human countenance), I say, being thus curtailed and cut
off in my classical learning, I must confess I managed to pick up a pretty smattering of genteel
information from that treasury of all sorts of knowledge, at least sufficient to make me a match in
learning for all the noblemen and gentlemen who came to our house. Well, on looking over the "Flare-
up" notices to correspondents, I read, one day last April, among the notices, as follows:—
"'Automodon.' We do not know the precise age of Mr. Baker, of Covent Garden Theatre; nor are we
aware if that celebrated son of Thespis is a married man.
"'Ducks and Green-peas' is informed, that when A plays his rook to B's second Knight's square, and B,
moving two squares with his Queen's pawn, gives check to his adversary's Queen, there is no reason
why B's Queen should not take A's pawn, if B be so inclined.
"'F. L. S.' We have repeatedly answered the question about Madame Vestris: her maiden name was
Bartolozzi, and she married the son of Charles Mathews, the celebrated comedian.
"'Fair Play.' The best amateur billiard and écarté player in England, is Coxe Tuggeridge Coxe, Esq., of
Portland Place, and Tuggeridgeville: Jonathan, who knows his play, can only give him two in a game of
a hundred: and at the cards, no man is his superior. Verbum sap.
"'Scipio Americanus' is a blockhead."
I read this out to the Count and Tagrag, and both of them wondered how the Editor of that tremendous
Flare-up should get such information; and both agreed that the Baron, who still piqued himself absurdly
on his play, would be vastly annoyed by seeing me preferred thus to himself. We read him the
paragraph, and preciously angry he was. "Id is," he cried, "the tables (or 'de dabels,' as he called them),
de horrid dabels; gom viz me to London, and dry a slate-table, and I vill beat you." We all roared at
this; and the end of the dispute was, that, just to satisfy the fellow, I agreed to play his Excellency at
slate-tables, or any tables he chose.
"Gut," says he, "gut; I lif, you know, at Abednego's, in de Quadrant; his dabels is goot; ve vill blay dere,
if you vill;" and I said, I would: and it was agreed that, one Saturday night, when Jemmy was at the
Opera, we should go to the Baron's rooms, and give him a chance.
We went, and the little Baron had as fine a supper as ever I saw; lots of champagne (and I didn't mind
drinking it), and plenty of laughing and fun. Afterwards, down we went to billiards. "Is dish Mishter
Coxsh, de shelebrated player?" says Mr. Abednego, who was in the room, with one or two gentlemen of
his own persuasion, and several foreign noblemen, dirty, snuffy, and hairy, as them foreigners are. "Is
dish Mishter Coxsh? blesh ma hart, it is a honer to see you, I have heard so much of your play."
"Come, come," says I, "sir;" for I'm pretty wide awake; "none of your gammon; you're not going to
hook me."
"No, begar, dis fish you not catch," says Count Mace.
"Dat is gut! haw! haw!" snorted the Baron: "hook him! lieber himmel, you might dry and hook me as
well. Haw! haw!"
Well, we went to play. "Fife to four on Coxe," screams out the Count.—"Done and done," says another
nobleman. "Ponays," says the Count.—"Done," says the nobleman. "I vill take your six crowns to four,"
says the Baron.—"Done," says I; and, in the twinkling of an eye, I beat him;—once making thirteen off
the balls without stopping.
We had some more wine after this; and if you could have seen the long faces of the other noblemen, as
they pulled out their pencils and wrote I O U's for the Count. "Va toujours, mon cher," says he to me,
"you have von for me tree hundred pounds."
"I'll blay you guineas dis time," says the Baron. "Zeven to four you must give me, though;" and so I did:
and in ten minutes that game was won, and the Baron handed over his pounds. "Two hundred and sixty
more, my dear, dear Coxe," says the Count; "you are mon ange gardien!" "Wot a flat Mishter Coxsh ish,
not to back his luck," I heard Abednego whisper to one of the foreign noblemen.
"I'll take your seven to four, in tens," said I to the Baron. "Give me three," says he, "and done." I gave
him three, and lost the game by one. "Dobbel, or quits," says he. "Go it," says I, up to my mettle; "Sam
Coxe never says no;"—and to it we went. I went in, and scored eighteen to his five. "Holy Moshesh!"
says Abednego, "dat little Coxsh is a vonder! who'll take odds?"
"I'll give twenty to one," says I, "in guineas."
"Ponays, yase, done," screams out the Count.
"Bonies, done," roars out the Baron: and before I could speak, went in, and, would you believe it?—in
two minutes he somehow made the game!

Oh, what a figure I cut when my dear Jemmy heard of this afterwards!—In vain I swore it was guineas:
the Count and the Baron swore to ponies; and when I refused, they both said their honour was
concerned, and they must have my life, or their money. So when the Count showed me actually that, in
spite of this bet (which had been too good to resist) won from me, he had been a very heavy loser by
the night; and brought me the word of honour of Abednego, his Jewish friend, and the foreign
noblemen, that ponies had been betted;—why, I paid one thousand pounds sterling of good and lawful
money;—but I've not played for money since: no, no; catch me at that again, if you can.

MAY. [1840.
 MEMBERS OF THE LONDON PRESS.
A BENEFIT. WEATHER.
"Sich a Gettin up Stairs." while forced
his dwindling
Sweet Gallery squeeze, you will possess victims
The utmost freedom of the press; to confess,
Crowds, looking up, still pushing go,
With stares above, and stairs below;
The soldier first, a foremost man,
Like Bow-street culprits—keeps the van,
Charges the door, whose keepers stern
A "bob" will charge him in return;
He's got his step, so with light mind
Bears all the pressure from behind;
Feels from the rear-mob, all alive,
A drive, though not a carriage drive:
And, lo! among them, soot-grimed deep,
A sweep, though not a carriage sweep.
Baker and butcher, lass and lover;
With one fat Falstaff falling over,
A Carriage Sweep.
Sure—though he like it not—to go
"small by
And lump it when he gets below;
degrees, and
A prize John Bull, who, bulky dunce,
beautifully
Takes both alternatives at once,
less."
And quickly reaches his first floor,
Dismounted at the Gallery Door!

408. Portrait
4. Exhibition of the Royal Academy
of the
opens, at the National Gallery.
President. ☞

R.A.'s are raised to power: and, presto, bang!

"On inner walls the cry is still 'they hang;'"
While many a heavy sigh the artists fetch,
"To have them hang our pictures is no ketch."
For half their sins did justice prompt the elves,
Half the R.A. array would hang themselves!

409. Red Deer, after Landseer.

MAY—A new drop scene at the Opera.
 MAY.—A New Drop Scene at the Opera.
No lady is a lady without having a box at the Opera: so my Jemmy, who knew as much about music,—
bless her!—as I do about sanscrit, algebra, or any other foreign language, took a prime box on the
second tier. It was what they called a double box; it really could hold two, that is, very comfortably; and
we got it a great bargain—for five hundred a year! Here, Tuesdays and Saturdays we used regularly to
take our places, Jemmy and Jemimarann sitting in front; me, behind: but as my dear wife used to wear
a large fantail gauze hat, with ostrich feathers, birds of paradise, artificial flowers, and tags of muslin or
satin, scattered all over it, I'm blest if she didn't fill the whole of the front of the box; and it was only by
jumping and dodging, three or four times in the course of the night, that I could manage to get a sight
of the actors. By kneeling down, and looking steady under my darling Jemmy's sleeve, I did contrive,
every now and then, to have a peep of Senior Lablash's boots, in the Puritanny, and once saw Madame
Greasi's crown and head-dress in Annybalony.
What a place that Opera is, to be sure! and what enjoyments us aristocracy used to have! Just as you
have swallowed down your three courses (three curses I used to call them; for so, indeed, they are,
causing a deal of heartburns, headaches, doctor's bills, pills, want of sleep, and such like)—just, I say,
as you get down your three courses, which I defy any man to enjoy properly, unless he has two hours
of drink and quiet afterwards, up comes the carriage, in bursts my Jemmy, as fine as a duchess, and
scented like our shop. "Come, my dear," says she, "it's Normy to-night (or Annybalony, or the Nosey di
Figaro, or the Gazzylarder, as the case may be); Mr. Coster strikes off punctually at eight, and you know
it's the fashion to be always present at the very first bar of the aperture;" and so off we budge, to be
miserable for five hours, and to have a headache for the next twelve, and all because it's the fashion!
After the aperture, as they call it, comes the opera, which, as I am given to understand, is the Italian
for singing. Why they should sing in Italian, I can't conceive; or why they should do nothing but sing:
bless us, how I used to long for the wooden magpie in the Gazzylarder, to fly up to the top of the
church-steeple, and see the chaps with the pitchforks to come in and carry off that wicked Don June.
Not that I don't admire Lablash, and Rubini, and his brother, Tomrubini, him who has that fine bass
voice, I mean, and acts the Corporal in the first piece, and Don June in the second; but three hours is a
little too much, for you can't sleep on those little rickety seats in the boxes.
The opera is bad enough; but what is that to the bally? You should have seen my Jemmy the first night
when she stopped to see it; and when Madamsalls Fanny and Theresa Hustler came forward, along with
a gentleman, to dance, you should have seen how Jemmy stared, and our girl blushed, when Madamsall
Fanny, coming forward, stood on the tips of only five of her toes, and raising up the other five, and the
foot belonging to them, almost to her shoulder, twirled round, and round, and round, like a teetotum,
for a couple of minutes or more; and as she settled down, at last, on both feet, in a natural decent
posture, you should have heard how the house roared with applause, the boxes clapping with all their
might, and waving their handkerchiefs; the pit shouting, "Bravo!" Some people, who, I suppose, were
rather angry at such an exhibition, threw bunches of flowers at her; and what do you think she did?
why, hang me, if she did not come forward, as though nothing had happened, gather up the things they
had thrown at her, smile, press them to her heart, and began whirling round again, faster than ever!—
Talk about coolness, I never saw such in all my born days.
"Nasty thing!" says Jemmy, starting up in a fury; "if women will act so, it serves them right to be treated
so."
"O, yes! she acts beautifully," says our friend, his Excellency, who, along with Baron von Punter, and
Tagrag, used very seldom to miss coming to our box.
"She may act very beautifully, Munseer, but she don't dress so; and I am very glad they threw that
orange-peel and all those things at her, and that the people waved to her to get off."
Here his Excellency, and the Baron, and Tag, set up a roar of laughter. "My dear Mrs. Coxe," says Tag,
"those are the most famous dancers in the world; and we throw myrtle, geraniums, and lilies, and
roses, at them, in token of our immense admiration!"
"Well, I never!" said my wife; and poor Jemimarann slunk behind the curtain, and looked as red as it
almost. After the one had done, the next begun; but when, all of a sudden, a somebody came skipping
and bounding in, like an Indian-rubber ball, flinging itself up at least six feet from the stage, and there
shaking about its legs like mad, we were more astonished than ever!
"That's Anatole," says one of the gentlemen.
"Anna who?" says my wife, and she might well be mistaken; for this person had a hat and feathers, a
bare neck and arms, great black ringlets, and a little calico frock, which came down to the knees.
"Anatole; you would not think he was sixty-three years old, he's as active as a man of twenty."
"He!" shrieked out my wife; "what, is that there a man? For shame! Munseer. Jemimarann, dear, get
your cloak, and come along; and I'll thank you, my dear, to call our people and let us go home."
You wouldn't think, after this, that my Jemmy, who had shown such a horror at the bally, as they call it,
should ever grow accustomed to it; but she liked to hear her name shouted out in the crush-room, and
so would stop till the end of everything; and, law bless you! in three weeks from that time she could
look at the ballet as she would at a dancing-dog in the streets, and would bring her double-barrelled
opera-glass up to her eyes as coolly as if she had been a born duchess. As for me, I did at Rome as
Rome does, and precious fun it used to be, sometimes.
My friend the Baron insisted, one night, on my going behind the scenes, where, being a subscriber, he
said I had what they call my ontray. Behind then I went; and such a place you never saw nor heard of!
Fancy lots of young and old gents, of the fashion, crowding round and staring at the actresses
practising their steps. Fancy yellow, snuffy foreigners, chattering always, and smelling fearfully of
tobacco. Fancy scores of Jews, with hooked noses, and black muzzles, covered with rings, chains, sham
diamonds, and gold waistcoats. Fancy old men, dressed in old night-gowns, with knock-knees, and dirty
flesh-coloured cotton stockings and dabs of brickdust on their wrinkled old chops, and tow wigs (such
wigs!) for the bald ones, and great tin spears in their hands, mayhap, or else shepherd's crooks, and
fusty garlands of flowers, made of red and green baize! Fancy troops of girls, giggling, chattering,
pushing to and fro, amidst old black canvas, Gothic halls, thrones, pasteboard Cupids, dragons, and
such like; such dirt, darkness, crowd, confusion, and gabble of all conceivable languages was never
known!
If you could but have seen Munseer Anatole! Instead of looking twenty, he looked a thousand. The old
man's wig was off, and a barber was giving it a touch with the tongs; Munseer was taking snuff himself,
and a boy was standing by, with a pint of beer from the public-house at the corner of Charles-street.
I met with a little accident, during the three-quarters of an hour which they allow for the entertainment
of us men of fashion on the stage, before the curtain draws up for the bally, while the ladies in the
boxes are gaping, and the people in the pit are drumming with their feet and canes in the rudest
manner possible, as though they couldn't wait.
Just at the moment before the little bell rings, and the curtain flies up, and we scuffle off to the sides
(for we always stay till the very last moment), I was in the middle of the stage, making myself very
affable to the fair figgerantys which was spinning and twirling about me, and asking them if they wasn't
cold, and such like politeness, in the most condescending way possible, when a bolt was suddenly
withdrawn, and down I popped, through a trap in the stage, into the place below. Luckily, I was
stopped by a piece of machinery, consisting of a heap of green blankets, and a young lady coming up as
Venus rising from the sea. If I had not fallen so soft, I don't know what might have been the
consequence of the collusion. I never told Mrs. Coxe, for she can't bear to hear of my paying the least
attention to the fair sex.
JUNE—Striking a balance.
 GAME IN SEASON.
2. Epsom Races.—"Surrey for the Field."

ROULETTE AT EPSOM.—Tent Scene.

I'm very ill; my circulation halts

I' the blood;
Soh! shall I take a dose of Epsom salts,
Or forego Epsom salts for Epsom races?
I chose the trip before the physic-sipping,
And very prettily I paid for tripping! Death of
Desdemona.
"Start fair," I cried,—I'd often started fowl
Out of the Moors,—but then I did start fair:
Foul—from the Moor.
The Course of course I reach'd, and cheek by jowl
Was standing with my betters, gazing there
At a horse winning at his jockey's beck, How hard
As felons win the gallows—by a neck! to
bear-o,
"Tak tent!" the Scotchman says, that's "look about," ♌♄☿♒
But, "take care of the tent," he should have said: Faro
I went within, and wish I'd gone without that's
A stake, or had a good rump-steak instead; unfair-o.
But I had cash, and having made a set
At them, and they at me, slap at Roulette.

And if 'twas natural to have gone within,

I soon discovered it was very flat:
A sovereign good for me it would have been
If I had had no sovereigns,—verbum sat! High game.
I lost!—and took no note when all was done,
Except a note of how much they had won!

I cannot say they were a dirty set,

Because they clean'd me so completely out;
A bout like this of Epsom Downs' roulette
Teaches a mortal what he is about.
Cheating is physic.—While the game's alive
It empties pockets if it doesn't thrive!

5. Boniface, (first Alderman of Port-soken?)

12. Mr. Wakley declared, that Gin was his best friend—it was equal to 1000
inquests a year.
A Palace reared! and lo! in quest of gin,
Thousands, sans scruple, pass for drams within;
Water they'd spurn, e'en from Geneva's lake,
Gin ever—not Geneva's—they will take:
In quest of that, when they no more can run,
Wakley his inquest holds, and all is done! Cordial reception.
Caught in his own
JUNE.—Striking a Balance. gin.
Next door to us, in Portland-place, lived the Right Honourable the Earl of
Kilblazes, of Kilmacrasy Castle, county Kildare, and his mother, the Dowager Countess. Lady Kilblazes
had a daughter, Lady Juliana Matilda Mac Turk, of the exact age of our dear Jemimarann; and a son,
The Honourable Arthur Wellington Anglesea Blucher Bulow Mac Turk, only ten months older than our
boy, Tug.
My darling Jemmy is a woman of spirit, and, as became her station, made every possible attempt to
become acquainted with the Dowager Countess of Kilblazes, which her ladyship (because, forsooth, she
was the daughter of the Minister, and the Prince of Wales's great friend, the Earl of Portansherry)
thought fit to reject. I don't wonder at my Jemmy growing so angry with her, and determining, in every
way, to put her ladyship down. The Kilblazes' estate is not so large as the Tuggeridge property, by two
thousand a-year, at least; and so my wife, when our neighbours kept only two footmen, was quite
authorized in having three; and she made it a point, as soon as ever the Kilblazes' carriage-and-pair
came round, to have her own carriage-and-four.
Well, our box was next to theirs at the Opera; only twice as big. Whatever masters went to Lady
Juliana, came to my Jemimarann; and what do you think Jemmy did? she got her celebrated governess,
Madam de Flicflac, away from the Countess, by offering a double salary. It was quite a treasure, they
said, to have Madame Flicflac; she had been (to support her father, the Count, when he emigrated) a
French dancer at the Italian Opera. French dancing, and Italian, therefore, we had at once, and in the
best style: it is astonishing how quick and well she used to speak—the French especially.
Master Arthur Mac Turk was at the famous school of the Reverend Clement Coddler, along with a
hundred and ten other young fashionables, from the age of three to fifteen; and to this establishment
Jemmy sent our Tug, adding forty guineas to the hundred and twenty paid every year for the boarders.
I think I found out the dear soul's reason, for, one day, speaking about the school to a mutual
acquaintance of ours and the Kilblazes, she whispered to him, that "she never would have thought of
sending her darling boy at the rate which her next-door neighbour paid; their lad, she was sure, must
be starved: however, poor people! they did the best they could on their income."
Coddler's, in fact, was the tip-top school near London; he had been tutor to the Duke of Buckminster,
who had set him up in the school, and, as I tell you, all the peerage and respectable commoners came
to it. You read in the bill (the snopsis, I think Coddler called it), after the account of the charges for
board, masters, extras, &c.: "Every young nobleman (or gentleman) is expected to bring a knife and
fork, spoon, and goblet, of silver (to prevent breakage), which will not be returned; a dressing-gown
and slippers; toilet-box, pomatum, curling-irons, &c. &c. The pupil must, on NO ACCOUNT, be allowed to
have more than ten guineas of pocket-money, unless his parents particularly desire it, or he be above
fifteen years of age. Wine will be an extra charge; as are warm, vapour, and douche baths; carriage
exercise will be provided at the rate of fifteen guineas per quarter. It is earnestly requested that no
young nobleman (or gentleman) be allowed to smoke. In a place devoted to the cultivation of polite
literature, such an ignoble enjoyment were profane
"Clement Coddler, M.A.,
"Chaplain and late tutor to his Grace the
Duke of Buckminster.

"Mount Parnassus, Richmond, Surrey."

To this establishment our Tug was sent. "Recollect, my dear," said his mamma, "that you are a
Tuggeridge by birth, and that I expect you to beat all the boys in the school, especially that Wellington
Mac Turk, who though he is a lord's son, is nothing to you, who are the heir of Tuggeridgeville."
Tug was a smart young fellow enough, and could cut and curl as well as any young chap of his age; he
was not a bad hand at a wig either, and could shave, too, very prettily; but that was in the old time,
when we were not great people: when he came to be a gentleman, he had to learn Latin and Greek,
and had a deal of lost time to make up for on going to school.
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