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DOI: 10.1002/cctc.201500993 Communications

Ruthenium-Catalyzed Cross Metathesis of b-Myrcene and

its Derivatives with Methyl Acrylate
Arno Behr,* Leif Johnen, Andreas Wintzer, Arzu Gìmìş Çetin, Peter Neubert, and
Lutz Domke[a]

The reaction of b-myrcene with methyl acrylate produces 3-

methylenecyclopent-1-ene in the presence of the Ru catalyst
Neolyst M2 by ring-closing metathesis in the first step. In the
second step, the generated methylidene unit reacts with
methyl acrylate to give the corresponding unsaturated cyclic
ester by cross metathesis. Under the optimized reaction condi-
tions (80 8C, Neolyst M2, 16 equivalents of methyl acrylate), de-
rivatives of b-myrcene, myrcenol, myrcenyl acetate, and b-oci-
mene, react to yield functionalized acyclic esters.

Since its discovery by Banks and Bailey in 1964 when they re-
acted propylene with ethylene and 2-butene,[1] metathesis has
become powerful for both industrial applications[2] and aca-
demic research.[3] It constitutes an elegant route for direct C¢C
bond formation in organic chemistry,[3a,b] has a spectacular
Scheme 1. Metathesis of b-myrcene with methyl acrylate.
functional group tolerance, and Ru-catalyzed metathesis is
often a key step in the total synthesis of natural[4] and biologi-
cally active compounds.[5] cyclic pentenes.[10] Bilel and co-workers examined the cross
Furthermore, because of its convenient reaction regime, it is metathesis of several terpenes[11] such as citronellal, citronellol,
of great importance for industrial applications, and thus indus- and citral with methyl acrylate to form terpenoids using a Hov-
trially relevant compounds can be attained easily from bulk eyda catalyst.[12] The range of substrates was expanded by
chemicals in a single step.[6] The production of cyclohexadece- Mauduit to other terpenes, which included citronellene.[13]
none by Symrise, a flavor better known as Globanone, is an ex- However, for this substrate, which is similar to myrcene, an
ample of the successful application of metathesis. only moderate yield (< 25 %) could be realized. Quite recently,
To date, the metathesis of 1,3-dienes has been rarely report- Fomine et al. examined the metathesis of a- and b-pinene by
ed in the literature. Cossy and co-workers attained high che- computational modeling.[14] Nevertheless, to the best of our
moselectivities and yields in the cross metathesis of methyl knowledge, a cross metathesis of b-myrcene has not been de-
sorbate with 1-octene using a Hoveyda catalyst.[7] Additionally, scribed so far.
a structurally related substrate was reacted with styrene in the The demand for an easy access to unsaturated ester deriva-
presence of the Grubbs II catalyst.[8] With the use of this cata- tives, which show potential features as flavors and fragran-
lyst, the scope could be expanded to other functionalized ces,[15] has prompted us to undertake investigations in the field
dienes and reactants.[9] However, all of these examples have in of terpene functionalization. Herein, we present a hitherto un-
common that either high catalyst loadings (up to 5 mol %) or known derivatization of renewable b-myrcene with methyl ac-
long reaction times were required to achieve satisfactory rylate by a cross-metathesis reaction.
yields. Our initial studies were focused on the cross metathesis of
Previously, the 1,3-diene b-myrcene (Scheme 1) has been ex- b-myrcene with methyl acrylate (Scheme 1). Both C11-ester 1 a
amined exclusively in homometathesis to give functionalized and 1 b, respectively, derived from the direct cross metathesis,
were not formed in the presence of all tested Ru catalysts
(Table 1).
[a] Prof. Dr. A. Behr, Dr. L. Johnen, Dr. A. Wintzer, A. Gìmìş Çetin, P. Neubert,
Dr. L. Domke Instead, b-myrcene undergoes homometathesis to yield the
Department of Biochemical and Chemical Engineering ring-closed product (RCP), 3-methylenecyclopent-1-ene (2),[10, 16]
Technische Universit•t Dortmund which is ready to react with methyl acrylate to yield the corre-
Emil-Figge Strasse 66, 44227 Dortmund (Germany)
sponding cross-metathesis product, methyl 2-(cyclopent-2-en-
E-mail: [email protected]
1-ylidene)acetate (3). Although its synthesis has already been
Supporting Information and ORCID(s) from the author(s) for this article
are available on the WWW under http://dx.doi.org/10.1002/ suggested in a Horner–Wadsworth–Emmons reaction by Shiba-
cctc.201500993. saki et al.,[17] this compound has not been described so far. It

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Communications

Table 1. Precatalyst screening of the cross metathesis of b-myrcene and methyl acrylate at different temperatures.[a]

Entry Precatalyst Temperature

60 8C 80 8C 90 8C
X [%] Y(2) [%] Y(3) [%] X [%] Y(2) [%] Y(3) [%] X [%] Y(2) [%] Y(3) [%]
1 – – – – – – – – – –
2 Grubbs I 2 2 – 3 3 – 7 2 –
3 Grubbs II 68 56 1 98 62 13 97 63 13
4 Neolyst M2 8 7 - 95 67 14 94 65 10
5 Neolyst M2py 29 28 - 82 66 6 77 61 4
6[b] Neolyst M31 37 2 2 17 1 8 55 2 3
7[c] Neolyst M51 9 9 – 21 17 – 28 23 –

[a] 0.5 mol % precatalyst, c(b-myrcene) = 0.1 mol L¢1, b-myrcene/methyl acrylate = 1:4, t = 1 h, toluene; conversion and yields were detected by GC (Abbrevi-
ations of the precatalysts: see Figure 1). [b] Addition of 50.0 mol % PhSiCl3. [c] Addition of 0.5 mol % 0.1 m HCl. Abbreviations: X = conversion, Y = yield.

possesses a characteristic odor that can be described as Grubbs II catalyst. This observation was discussed previously
“green”, “buttery”, or “plastic”. by Grela et al. and is attributed to an easier dissociation of the
Among the various Ru precatalysts tested were those dem- benzylidene in Grubbs II than the indenylidene in Neolyst
onstrated previously to be successful in metathesis, such as M2.[19]
first- and second-generation Grubbs catalysts and representa- The structurally related catalyst, Neolyst M2py, which has
tives of the Neolyst family (Figure 1). The main results of the one chlorine and the phosphine ligand is substituted by pyri-
screening of different precatalysts are presented in Table 1. dine, also demonstrated a good activity for the homometathe-
sis to yield 2 in 66 %, but less of product 3 was ob-
tained (entry 5). Surprisingly, a reaction performed
with Neolyst M31 resulted in low amounts of the de-
sired products at all temperatures (entry 6). Signifi-
cant differences between the conversion and yield in-
dicated polymeric side reactions, for example, the
ring-opening polymerization of cyclic diene 2. This
phenomenon was described by Sita in the polymeri-
zation of citronellene.[10a] Products derived from an
acyclic diene metathesis of the substrate were not
observed in all runs is in accordance with the results
of Fogg et al. for highly dilute solutions.[20] The results
from experiments in which Neolyst M51 was used as
the precatalyst are in line with the work of Grela
et al.,[21] as it is not thermally stable enough to per-
form ring-closing metathesis efficiently.
Figure 1. Selected Ru precatalysts for the cross metathesis of b-myrcene (Cy = cyclohexyl,
Mes = mesityl). Encouraged by the results with Neolyst M2, differ-
ent solvents were screened. With regard to the econ-
omy and eco-friendly credentials of metathesis,
The experiments were started at 60 8C, and only the reaction which usually works with expensive transition-metal catalysts
with the Grubbs II catalyst gave a satisfactory conversion (X) of synthesized in multistep reactions, the choice of the right sol-
b-myrcene with a good yield (Y) to the cyclic homometathesis vent is essential. In particular, a suitable solvent could facilitate
product 2 of 56 %, whereas only traces of the cyclic C7-ester 3 the recovery of the catalyst and would offer a better product
could be detected in the final mixture (entry 3). However, a re- separation. The results for the solvent screening are shown in
action with the structurally similar precatalyst Neolyst M2,[18] Figure 2.
which bears an indenylidene at the metal center instead of Among a number of solvents, the catalyst showed a compa-
benzylidene, gave the diene 2 only in poor yield (7 %, entry 4). rable activity and selectivity for the desired products in tolu-
If the reaction temperature was increased to 80 8C, an en- ene, heptane, and 1,4-dioxane. More polar solvents such as
hanced conversion was noted in all cases. Using Grubbs II and methyl tert-butyl ether (MTBE) and THF have worse characteris-
Neolyst M2 catalysts led to similar results with almost full con- tics towards the reaction, and only traces of the cyclic ester
version after 1 h and a yield of the diene 2 of 62 and 67 %, re- were formed. In contrast to the low-boiling-point solvents,
spectively. Fortunately, in addition to the homometathesis only propylene carbonate (PC, high boiling) has the ability to
product, the ester 3 could be detected in up to 14 % yield. A give 2 and its consecutive product 3 in promising yields. With
comparison of both runs showed that Neolyst M2 required regard to a beneficial product separation by distillation, this
higher temperatures to attain a similar activity to that of the solvent has to be considered.[22] Furthermore, no reaction took

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Communications
Furthermore, the dependence on the amount of methyl ac-
rylate was examined in the hope to promote the reaction in
favor of either diene 2 or cyclic ester 3. The results are illustrat-
ed in Figure 4.

Figure 2. Optimization of the solvent in the cross metathesis of b-myrcene

with methyl acrylate. Conditions: 0.5 mol % Neolyst M2, c(b-myrcene) = 0.1
mol L¢1, b-myrcene/methyl acrylate = 1:4, T = 80 8C or reflux, t = 1 h; conver-
sions and yields were detected by GC (MTBE = methyl tert-butyl ether,
NMP = N-methyl-2-pyrrolidone, PC = propylene carbonate). Abbreviations:
X = conversion, Y = yield.

place in solvents such as dichloromethane, methanol, DMSO,

and ethylene glycol. Figure 4. Optimization of the b-myrcene/methyl acrylate molar ratio in the
Our attention was then focused on the variation of the cata- cross metathesis of b-myrcene with methyl acrylate. Conditions: 0.5 mol %
lyst loading to minimize side reactions and thus to force the Neolyst M2, c(b-myrcene) = 0.1 mol L¢1, T = 80 8C, t = 1 h, toluene; conversion
and yields were detected by GC. Abbreviations: X = conversion, Y = yield.
final cross metathesis to give 3 using toluene as the solvent
(Figure 3). It may be assumed that an enhanced concentration
of the active catalyst will promote the second reaction step of An increase of the ratio of b-myrcene to methyl acrylate
the cross metathesis with methyl acrylate. from 1:4 to 1:8 and finally to 1:16 gave an improved yield for
the consecutive product 3 of up to 20 %, as expected. The use
of methyl acrylate in a great excess, such as 1:32 or even 1:64,
seems to inhibit the reaction and both the homo- and cross-
metathesis products were detected in lower amounts. At
a lower ratio of only 1:2, more diene 2 (74 %) and less C7-ester
3 (5 %) were formed. Consequently, if no methyl acrylate is
added to the reaction, a maximum yield of 86 % of 2 was de-
tected.
Indeed, with the application of a combination of both steer-
ing effects, a catalyst concentration of 1.5 mol % and an excess
of methyl acrylate of 16:1 gave a 22 % yield of the ring-closing
metathesis product and a maximum of 42 % for the corre-
sponding cyclic ester 3.
Figure 3. Optimization of the catalyst loading in the cross metathesis of b- With regard to the economy of this reaction, we tried to op-
myrcene with methyl acrylate. Conditions: Neolyst M2, c(b-myrcene) = 0.1 timize the space time yield by increasing the substrate concen-
mol L¢1, b-myrcene/methyl acrylate = 1:4, T = 80 8C, t = 1 h, toluene; conver-
tration (Figure 5).
sion and yields were detected by GC. Abbreviations: X = conversion,
Y = yield. An enhanced b-myrcene concentration (up to 0.5 mol L¢1)
has no significant influence on reactivity and selectivity. How-
ever, if the reaction mixture is more concentrated, the conver-
If the concentration of the precatalyst is doubled to 1 mol %,
the detected amount of 3-methylenecyclopent-1-ene (2) in the
final mixture decreased, whereas the yield of the cyclic ester 3
increased. A further increase of the catalyst concentration to
1.5 mol % affected the homometathesis but generated the
consecutive product in up to 35 % yield. Unfortunately, this
trend was not observed using 2 mol % of Neolyst M2. Indeed,
despite the full conversion, less of the ring-closing metathesis
product 2 and less of the cross-metathesis product 3 were
generated. It can be supposed that Neolyst M2 catalyzes the
ring-opening metathesis polymerization (ROMP)[23] of 2 in addi-
tion to the ring-closing metathesis of b-myrcene to give 3. If
Figure 5. Optimization of the b-myrcene concentration in the cross metathe-
0.25 mol % of the catalyst was employed, the conversion de-
sis of b-myrcene with methyl acrylate. Conditions: 0.5 mol % Neolyst M2, b-
creased, but a higher selectivity for the diene (54 %) was ach- myrcene/methyl acrylate = 1:4, T = 80 8C, t = 1 h, toluene; conversion and
ieved. Unfortunately, no cyclic ester could be detected. yields were detected by GC. Abbreviations: X = conversion, Y = yield.

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Communications
sion and thus the yield for both products decreased. Possibly, myrcene. Indeed, the direct cross-metathesis product is gener-
at higher concentrations, a catalyst deactivation occurs caused ated in all cases, however, the formation of Diels–Alder ad-
by substrate inhibition. At a low concentration of 0.05 mol L¢1, ducts (DAA) was also detected. An increase of the catalyst
the yield for the homometathesis product could be slightly im- loading from 0.5 to 3 mol % led to an increased conversion to
proved (70 %), but surprisingly, no ring-closed product was ob- 23 % to give the ester 4 in a maximum 4 % yield (entries 1–3).
tained. If the excess of methyl acrylate was increased to 1:16, 14 % of
These results illustrated that the reaction path of an intra- the desired product could be detected (entry 4). Remarkably,
molecular homometathesis (to give 2) is much faster than the a further enhancement of the acrylate and an increased reac-
direct cross metathesis of b-myrcene itself (to give 1 a,b). To tion time (entries 5 and 6, respectively) promoted the unde-
prevent the ring-closing reaction, the (isolated) threefold sub- sired Diels–Alder reaction.
stituted double bond was functionalized so that the remaining Additionally, myrcenyl acetate was used in the reaction, and
diene unit of the molecule can react exclusively with the reac- the results are given in Table 3.
tant. Therefore, myrcenol as well as its O-acetylated derivative,
myrcenyl acetate, were applied to the reaction. The latter was
synthesized by treatment of the alcohol with acetyl chloride in Table 3. Cross metathesis of myrcenyl acetate with methyl acrylate with
the presence of pyridine. Moreover, the reaction of isomeric b- Neolyst M2 in toluene.[a]
ocimene was examined (Figure 6).

Entry Precatalyst Myrcenyl acetate/ X Y(5) Y(DAA)

[mol %] methyl acrylate [%] [%] [%]
1 0.5 1:4 30 1 1
2 0.5 1:16 37 4 6
3 1.5 1:4 29 4 2

[a] Neolyst M2, c(myrcenyl acetate) = 0.1 mol L¢1, T = 80 8C, t = 3 h, tolu-
ene; conversion and yields were detected by GC. Abbreviations: X = con-
version, Y = yield.

Under the optimized reaction conditions, only traces of

Figure 6. Applied structurally related dienes for the cross metathesis with product 5 were detected (entry 1). Although the catalyst load-
methyl acrylate (double arrow: possible ring-closing metathesis reaction).
ing and/or amount of methyl acrylate were increased, only
a negligible yield for the cross-metathesis product was ob-
tained (entries 2 and 3). Clearly, the substituent of the sub-
The first investigations were undertaken with myrcenol, and strate seems to have a dramatic influence on the reaction. Pre-
the results of the reaction with methyl acrylate in the presence vious investigations by Hoye and Zhao[10b] on linalool showed
of Neolyst M2 are shown in Table 2. that a nucleophilic hydroxyl group is able to coordinate to the
All experiments were performed with Neolyst M2 in toluene metal center of the catalyst by substitution of a chlorine or
by adapting the reaction conditions from the reaction of b- phosphine to lead to an increased reaction rate. A non-nucleo-
philic acetyl function, which is present in myrcenyl acetate,
does not have these characteristics, which explains the low
conversion rates in a reaction with methyl acrylate.
Table 2. Cross metathesis of myrcenol with methyl acrylate with Neolyst As b-myrcene seemed to be highly reactive in ring-closing
M2 in toluene.[a]
metathesis, the isomer b-ocimene was taken into consideration
for direct cross metathesis with methyl acrylate. A mixture of
both the cis and trans isomers (cis/trans = 33:67) was first react-
ed in the presence of Neolyst M2 without any additional acry-
Entry Precatalyst Myrcenol/ X Y(4) Y(DAA)
late to give the corresponding methyl cyclopentadiene (6;
[mol %] methyl acrylate [%] [%] [%]
Scheme 2). The results of the temperature dependence of the
1 0.5 1:4 5 1 1 reaction are shown in Figure 7.
2 1.0 1:4 8 1 4
3 3.0 1:4 23 4 3 In accordance with the results for the cross metathesis of b-
4 3.0 1:16 44 14 8 myrcene (see above), the highest activity for Neolyst M2 was
5[b] 3.0 1:16 72 11 15 achieved at reaction temperatures above 80 8C, which yielded
6 3.0 1:32 59 9 13 up to 25 % of 6. In addition, it also indicated that a ring-closing
[a] Neolyst M2, c(myrcenol) = 0.1 mol L¢1, T = 80 8C, t = 1 h, toluene; con- reaction takes place for the cis rather than for the trans isomer,
version and yields were detected by GC. [b] t = 8 h. Abbreviations: X = which might be caused by the physical configuration/distance
conversion, Y = yield.
between the double bonds (Scheme 3). As a result, a maximum

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Communications

Table 4. Ring-closing metathesis of a cis/trans mixture of b-ocimene with

Neolyst M2 in toluene.[a]

Entry Precatalyst X(cis-ocimene) X(trans-ocimene) Y(6)

[%][mol %] [%][%] [%][%] [%][%]
1 0.1 36 24 4
2 0.3 62 27 13
Scheme 2. Ring-closing metathesis of a cis/trans mixture of b-ocimene.
3 0.5 94 33 24
4 1.0 99 49 25
5 1.5 99 59 24
6[b] 0.5 98 70 4

[a] Neolyst M2, c(b-ocimene) = 0.1 mol L¢1, T = 80 8C, t = 1 h, toluene; con-
versions and yield were detected by GC. [b] t = 16 h. Abbreviations: X =
conversion, Y = yield.

ing was examined (Table 4). An increased amount of Neolyst

M2 caused an increased conversion of both cis- and trans-oci-
mene. Simultaneously, the yield of 6 was increased to 25 %
using 1 mol % of the precatalyst (entry 4). Surprisingly, a pro-
longed reaction time improved the conversion but affected
the amount of product (4 %; entry 6). This observation can be
Figure 7. Optimization of the temperature in the homometathesis of b-oci-
explained by the fact that methyl cyclopentadiene might fur-
mene. Conditions: 0.5 mol % Neolyst M2, c(b-ocimene) = 0.1 mol L¢1, t = 1 h,
toluene; conversions and yield were detected by GC. Abbreviations: X = con- ther react in consecutive metathesis reactions (e.g., ROMP).
version, Y = yield. The special electronic situation of the double bond in b-oci-
mene (see above) allows a direct cross metathesis with methyl
acrylate to give the expected unsaturated acyclic ester 7.
of 41 % conversion was achieved for the trans isomer, whereas Moreover, the threefold substituted double bond reacts too to
a conversion of more than 94 % cis-ocimene was observed. give the corresponding product 8 with the dissociation of iso-
Furthermore, the conversion of b-ocimene is significantly butene. As a result of their configurations, several diastereo-
higher than the yield of the cyclic product. It is supposed that mers of 7 and 8 are possible. The results are summarized in
this is caused by the modified 1,3-diene unit in b-ocimene: the Table 5.
diene unit of b-myrcene contains two terminal double bonds. An increase of the reaction temperature from 60 to 90 8C
However, in b-ocimene an internal double bond is present promoted the conversion, and a maximum yield of the acyclic
next to the terminal one, which seems to affect the activity of esters 7 and 8 of 10 and 18 %, respectively, could be attained
the entire 1,3-diene unit towards homometathesis. Finally, b- (entries 1–3). If 1.5 mol % of the precatalyst was applied, the
ocimene is more able to react in an acyclic diene metathesis amounts of the desired products could only be improved
(ADMET), which is in agreement with the ring-closing metathe- slightly (entry 4).
sis and is one of the possible side reactions. Furthermore, the influence of an excess of methyl acrylate
To counteract those unintended reactions and simultaneous- was examined (Figure 8). With a b-ocimene/methyl acrylate
ly increase the yield of 6, the dependence of the catalyst load- ratio of 1:8 and 1:16, respectively, the highest yields of both

Scheme 3. Visualization of the reactivity of cis- and trans-ocimene in ring-closing metathesis.

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Communications

Table 5. Cross metathesis of a cis/trans mixture of b-ocimene with

Experimental Section
methyl acrylate with Neolyst M2 in toluene.[a]
Laboratory experiments
All experiments in this work were performed in an oxygen-free en-
vironment using standard Schlenk techniques. Typically, Neolyst
M2 (10.7 mg, 0.011 mmol, 1.5 mol %) and dry toluene (7.5 mL) were
placed in a 100 mL two-necked round-bottomed flask equipped
with a reflux condenser fitted with a bubble counter on top. The
Entry T [8C] X [%] Y(6) [%] Y(7) [%] Y(8) [%] mixture was then placed into an ultrasonic bath for 2 min until the
solid was dissolved completely. Subsequently, b-myrcene
1 60 49 4 2 6
(102.2 mg, 0.75 mmol, 1.0 equiv.) and methyl acrylate (1033.1 mg,
2 80 74 3 8 14
3 90 71 1 10 18 12.0 mmol, 16.0 equiv.) were added, and the flask was immersed in
4[b] 80 84 2 13 17 a preheated oil bath at the desired temperature (e.g., 80 8C). After
stirring for 1 h, the reaction was stopped by cooling to RT using an
[a] 0.5 mol % Neolyst M2, c(b-ocimene) = 0.1 mol L¢1, t = 1 h, toluene; con- ice bath, and the mixture was analyzed by GC using di-n-butyl
version and yields were detected by GC. [b] 1.5 mol % Neolyst M2. Abbre-
ether as the internal standard and isopropanol as an additional sol-
viations: X = conversion, Y = yield.
vent.

Chemicals
All nonaqueous solvents used in this work were purchased dry
from Acros Organics (Geel, Belgium) with a purity of 99 % or
higher. b-Myrcene was purchased from Acros Organics with
a purity of 90 %. Myrcenol and a cis/trans mixture of b-ocimene
(cis/trans = 33:67) were used in a purity of 98 % and were donated
by Givaudan (Vernier, Switzerland). Other chemicals were pur-
chased from commercial suppliers and were of the highest purity
available. They were used as received without further purification.
The Ru precatalysts denoted as “Neolyst” were donated by Umi-
core AG & Co. KG (Hanau, Germany). The Grubbs I and II precata-
lysts were purchased from Sigma Aldrich (St. Louis, Missouri, USA).
Figure 8. Optimization of the b-ocimene/methyl acrylate molar ratio in the
Ar gas (99.998 %) was purchased from Air Liquide Deutschland
cross metathesis of b-ocimene with methyl acrylate. Conditions: 0.5 mol % GmbH (Dìsseldorf, Germany) and was used as received.
Neolyst M2, c(b-ocimene) = 0.1 mol L¢1, t = 1 h, toluene; yields were detected
by GC. Abbreviations: X = conversion, Y = yield.
Analysis
Standard gas chromatographic analyses were performed by using
cross-metathesis products were attained. Interestingly, no
a HP 6890 instrument (Hewlett–Packard GmbH, Waldbronn, Germa-
cyclic diene was produced. Moreover, an excess of 1:32 seems ny) equipped with a flame ionization detector (FID, 300 8C) and
to inhibit the reaction as already confirmed for the reaction of a HP5 capillary column (30 m, diameter 0.32 mm, film thickness
b-myrcene (see above). A slight excess of methyl acrylate (1:2) 0.25 mm) connected to an autosampler. N2 was used as the carrier
affects the yields of the direct cross-metathesis products but gas. The injection volume of a sample was 1 mL.
also promotes the ring-closing reaction. GC–MS was performed by using a Hewlett–Packard 5973 instru-
In conclusion, we report the first access to methyl 2-(cyclo- ment (70 eV).
pent-2-en-1-ylidene)acetate from the reaction of renewable b-
All pure components were calibrated to determine the conversion
myrcene with methyl acrylate. This Ru-catalyzed tandem reac-
(X) of the reaction and yield (Y) of the products.
tion consists of a ring-closing metathesis of b-myrcene and
1
a subsequent cross metathesis with methyl acrylate and gives H and 13C NMR spectra were recorded by using a Bruker DRX400
a convenient access to cyclic C7-esters. Under the optimized re- (400 MHz for 1H and 101 MHz for 13C) and a Bruker DRX500
(500 MHz for 1H and 126 MHz for 13C) at RT (Bruker Corp., Billerica,
action conditions, a temperature of 80 8C, a catalyst loading
Massachusetts, USA). All chemical shifts d are given in ppm. Cou-
(Neolyst M2) of 1.5 mol %, and a methyl acrylate ratio of 1:16,
pling constants are indicated as J and given in Hz. References: TMS
the desired product was yielded in 42 %. Further systematic ex- (d = 0.00 ppm) was taken as internal standard. The chemical shift
aminations with other functionalized myrcene derivatives gave for deuterated chloroform CDCl3 is d = 7.26 ppm. Peak characteriza-
a detailed insight into the reaction pattern of the terpenyl scaf- tion: s = singlet, d = doublet, dd = double doublet, t = triplet, dt =
fold. As a result of their modified structures, myrcenol and double triplet, m = multiplet.
myrcenyl acetate were able to react directly in a cross meta-
thesis with methyl acrylate to give the corresponding acyclic
esters in up to 14 %. In the reaction of b-ocimene, both the Product isolation and characterization
cyclic diene and acyclic esters could be achieved with yields of 3-Methylenecyclopent-1-ene (2): The reaction mixture was puri-
25 and 18 %, respectively. fied by distillation to yield the desired product (bp = 82 8C) accord-

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 18673899, 2016, 3, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.201500993 by Ben Gurion University, Wiley Online Library on [21/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Communications
ing to Hoye et al.[10c] 1H NMR (500 MHz, CDCl3): d = 2.53 (m, 4 H, 136 (7), 121 (12), 105 (19), 91 (52), 79 (100), 77 (32), 67 (35), 65 (17),
2 CH2), 4.77 (s, 1 H, CH2¢HA), 4.86 (s, 1 H, CH2¢HB), 6.15 ppm (m, 2 H, 63 (7), 55 (33), 53 (20), 51 (16).
CH=CH); 13C NMR (126 MHz, CDCl3): d = 29.1 (CH2), 32.4 (CH2), 102.3
(=CH2), 134.6 (CH), 139.6 (CH), 155.2 ppm (C).
Acknowledgements
(E/Z)-Methyl 2-(cyclopent-2-en-1-ylidene)acetate ((E/Z)-3): The re-
action mixture was purified by column chromatography (silica This work was financially supported by the German Research
40 æ, cyclohexane/ethyl acetate 4:1) to yield the desired product Foundation (Deutsche Forschungsgemeinschaft DFG). The au-
as a cis/trans mixture (bp = 193 8C). 1H NMR (500 MHz, CDCl3): d = thors would like to thank Umicore AG&Co. KG for the donation
2.56 (m, 2 H, CH2), 2.95 (m, 2 H, CH2), 3.64 (s, 3 H, OCH3), 5.55 (s, 1 H,
of the ruthenium catalysts. We also thank Givaudan S.A. for the
CHCO2CH3 of the E isomer), 5.70 (s, 1 H, CHCO2CH3 of the Z isomer),
donation of myrcenol and b-ocimene.
6.23 (m, 1 H, CH), 6.55 ppm (m, 1 H, CH); 13C NMR (126 MHz, CDCl3):
d = 31.3 (CH2), 34.8 (CH2), 52.3 (OCH3), 109.7 (=CH2), 136.1 (CH),
149.7 (CH), 154.4 (C), 169.6 ppm (C=O); MS (EI, 70 eV): m/z (%): 139 Keywords: alkenes · C¢C coupling · homogeneous catalysis ·
(7), 138 (M+, 76), 123 (14), 108 (8), 107 (96), 106 (39), 105 (24), 95 metathesis · ruthenium
(26), 80 (8), 79 (77), 78 (48), 77 (100), 67 (20), 53 (14), 52 (14), 51
(29), 50 (18).
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