Subscriber access provided by TUFTS UNIV

Article
Multicomponent Synthesis of Diverse o-Arylated Benzamides
via o-Aminophenol (OAP) Directed C(sp2)-H Arylation
Yunyun Liu, Yi Zhang, and Jie-Ping Wan
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/[Link].7b01375 • Publication Date (Web): 02 Aug 2017
Downloaded from [Link] on August 2, 2017

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

The Journal of Organic Chemistry is published by the American Chemical Society.

1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 30 The Journal of Organic Chemistry

1
2
3
4
5
6
Multicomponent Synthesis of Diverse o-Arylated Benzamides via
7
8 o-Aminophenol (OAP) Directed C(sp2)-H Arylation
9
10
11 Yunyun Liu,* Yi Zhang and Jie-Ping Wan*
12
13
14 College of Chemistry and Chemical Engineering, Jiangxi Normal University,
15
16 Nanchang 330022, China
17
18
19 Email: chemliuyunyun@[Link]; wanjieping@[Link]
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35 ABSTRACT. o-Aminophenol (OAP) has been discovered as practical precursor of
36
37
38 directing group (DG) in the palladium-catalyzed aromatic C-H arylation of
39
40 benzamides. This newly identified, simple and low cost DG has exhibited broad
41
42
43 substrate tolerance in the rapid synthesis of various o-arylated benzamides via direct
44
45 assemblies of benzoyl chlorides, aryl iodides and different o-aminophenols in the
46
47
48 form of step economical multicomponent reaction.
49
50
51 INTRODUCTION
52
53
54 The C-H activation is inarguably one most powerful tool in modern
55
56 organic synthesis which plays crucial role in the areas of natural product
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 2 of 30

1
2
3
4 synthesis,1 drug discovery2 and material synthesis.3 Among the currently
5
6 known tactics enabling the C-H bond activation and functionalization, the
7
8
9 directed C-H activation wherein a DG is employed to assist the transformation
10
11 of latent C-H bond is regarded as the most widely applicable and reliable
12
13
14 protocol, since the presence of a proper DG is capable of inducing the
15
16 reaction selectivity and facilitating the bond transformation by stabilizing the
17
18
19 reaction intermediate.4 The past decade has witnessed spectacular progress in
20
21 the research of directed C-H activation reactions, and unprecedented
22
23
24 sophistication in the types, functions as well as innovative concepts around the
25
26 DG-based synthesis have been disclosed. Currently, a massive number of
27
28
29 different DGs, including the monodentate DG,5 bidentate DG,6 and many other
30
31 effective DGs7 are available for assisting the activation of C-H bonds of
32
33
34 different types.
35
36 In despite the notable advances in the DG-assisted C-H activation,
37
38
39 challenges also exist and remain yet to address. One of the major problems is
40
41
the rare availability of practical DG precursors with satisfactory stability and
42
43
44 low cost. The even more serious challenge is that most of the known directed
45
46
C-H activation reactions suffers from the cumbersome operations in installing
47
48
49 the DG to substrates and/or removing the DG from products. Therefore,
50
51
tremendous efforts have been made in recent years to overcome the problems of
52
53
54 the low atom economy resulting from the lengthy operation. Gratifyingly, a
55
56
57
variety of effective strategies and concepts, including traceless DG,4c,8
58
59
60
ACS Paragon Plus Environment
Page 3 of 30 The Journal of Organic Chemistry

1
2
3
4 deciduous DG,9 transient/catalytic DG10 and in situ DG generation11 etc have
5
6 been conceived and accomplished to guide more efficient directed C-H
7
8
9 activation reactions. However, considering the high cost, hard substructure
10
11 variation or limited application scope in the type of C-H bond transformation,
12
13
14 developing new bidentate DG which address one or more of these restrictions is
15
16 still highly desirable to complement the chemistry of directed C-H activation.
17
18
19 During our efforts in developing step-efficient C-H activation reactions,
20
21 we have reported in 2015 the 8-aminoquinoline (AQ) directed benzamide Ar-H
22
23
24 arylation reactions by the in situ DG installation, which represents the first
25
26 example free-of prior DG installation in AQ directed C-H activation reactions.12
27
28
29 Under the inspiration of this work, the γ-C-H arylation of phenylacetamides,13
30
31 the β-C(sp3)-H arylation of alkyl amides14 and the o-sulfenylation of the Ar-H
32
33
34 bond(s) in bemzamides15 have been consequently realized. While the general
35
36 applicability of such tandem reaction-based C-H arylation has been gradually
37
38
39 validated, the high cost and limited variability of the AQ remain as issues
40
41
requiring further improvement.16 Based on our sustaining efforts in devising
42
43
44 facile and practical C-H activation reactions, we report herein the first example
45
46
of the OAP directed ortho-arylation of the Ar-H bond(s) in the in situ generated
47
48
49 benzamides via three-component reactions of o-aminophenols, benzoyl
50
51
chlorides and aryl iodides. The o-aminophenols act as the DG precursors in the
52
53
54 reactions which display advantages not only in the quite easy availability and
55
56
57
low cost, but also in the direct utility without any prior elaboration as well as
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 4 of 30

1
2
3
4 the easy variation in substructure for the synthesis of products containing
5
6 diverse OAP fragments.
7
8
9 RESULTS AND DISCUSSION
10
11
12 To begin the work, the reaction of OAP (1a), benzoyl chloride (2a) and
13
14
15 p-methoxy iodobenzene (3a) was tentatively run in the presence of Pd(OAc)2 and
16
17 K2CO3 in heating toluene, from which fair yield of the C-H arylated product 4a was
18
19
20 successfully observed with different catalyst loading (entries 1-3, Table 1).
21
22 Subsequent efforts in employing different palladium reagents did not lead to the
23
24
25 improvement in the yield of 4a (entries 4-7, Table 1). Altering the base additive of
26
27 different properties gave no better result, either (entries 8-12, Table 1). Notably,
28
29
30 increasing the amount of K2CO3 from 2 equiv. to 4 equiv. enabled the production of
31
32 4a with evidently higher yield (entries 13-15, Table 1), which could be ascribed to the
33
34
35 extra base consumption in promoting the in situ amidation between 1a and 2a.
36
37 Interestingly, further investigation in screening the reaction medium using solvents
38
39
40 such as p-xylene, dioxane, DCM, DMSO and MeCN proved that MeCN was a good
41
42 medium for the C-H activation reaction by affording 4a with even enhanced yield
43
44
45 (entries 16-20, Table 1).
46
47
48 Table 1 Optimization on the OAP directed Ar-H arylationa
49
50
I
51 O
OH
52 Cl
Pd cat., base
solvent, T
53 NH2
OMe MeO O OAP OMe
54 1a 2a 3a
4a
55
56
57 Entry Catalyst Base Solvent Yieldb (%)
58
59
60
ACS Paragon Plus Environment
Page 5 of 30 The Journal of Organic Chemistry

1
2
3 1 Pd(OAc)2 K2CO3 toluene 37
4
5
2c Pd(OAc)2 K2CO3 toluene 35
6
7
8 3d Pd(OAc)2 K2CO3 toluene 22
9
10 4 PdCl2 K2CO3 toluene 32
11
12 5 Pd(Ph3P)4 K2CO3 toluene 36
13
14
6 Pd/C K2CO3 toluene trace
15
16
17 7 PdCl2(Ph3P)2 K2CO3 toluene 34
18
19 8 Pd(OAc)2 Cs2CO3 toluene 21
20
21 9 Pd(OAc)2 NaHCO3 toluene trace
22
23
10 Pd(OAc)2 t-BuOK toluene 20
24
25
26 11 Pd(OAc)2 NaOH toluene trace
27
28 12 Pd(OAc)2 DBU toluene trace
29
30 13e Pd(OAc)2 K2CO3 toluene 51
31
32
33
14f Pd(OAc)2 K2CO3 toluene 66
34
35 15g Pd(OAc)2 K2CO3 toluene 65
36
37 16f Pd(OAc)2 K2CO3 p-xylene 24
38
39 17f Pd(OAc)2 K2CO3 1,4-dioxane 30
40
41
42
18f Pd(OAc)2 K2CO3 CH3CN 87
43
44 19f Pd(OAc)2 K2CO3 DCM trace
45
46 20f Pd(OAc)2 K2CO3 DMSO trace
47
48 a
General conditions: 1a (0.3 mmol), 2a (0.3 mmol), 3a (0.9 mmol), catalyst (5 mol%),
49
50 base (0.6 mmol), solvent (2 mL), stirred at 110 oC or reflux (heating at 90 oC) for 12
51 h. bIsolated yield. cPd(OAc)2 (10 mol%). dPd(OAc)2 (3 mol%). eK2CO3 (0.9 mmol).
52 f
53 K2CO3 (1.2 mmol). gK2CO3 (1.5 mmol).
54
55 To disclose the scope of this one-pot C-H arylation protocol, the entries
56
57
58 employing 1a, various benzoyl chlorides without or with para-substitution, and
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 6 of 30

1
2
3
4 different aryl iodides were examined. As showing in Table 2, this double C-H
5
6 arylation reaction displayed broad tolerance to both the benzoyl chloride and aryl
7
8
9 idodide components. While conventional functional groups with both electron
10
11 withdrawing and donating property in the substrates smoothly took part in the
12
13
14 synthesis, the entry employing strong electron withdrawing group such nitro
15
16 functionalized aryl iodide was found to give corresponding product (4k, Table 2) with
17
18
19 slightly lower yield, all other entries provided the double arylated benzamides 4 with
20
21 excellent yield, demonstrating the high efficiency of OAP as DG in this double C-H
22
23
24 arylation reaction. Notably, the X-ray single crystal diffraction on 4b was conducted
25
26 to confirm the products structure on the basis of other spectral analysis (see Fig. S1 in
27
28
29 the SI for the ORTEP structure).17 Further efforts in individual experiment examining
30
31 other coupling reagents, including bromobenzene, 4-bromoacetophenone,
32
33
34 2-bromopyridine, 2-iodothiophene and PhOTs did not provide the expect C-H
35
36 arylated product. What’s more, the primary effort in derivation of the model
37
38
39 compound 4a via intramolecular C-N bond construction was made, however,
40
41
following the catalytic method in literature,19 no expect cyclised product was
42
43
44 provided.
45
46
47 Table 2 Scope of the one-pot double C-H arylationa
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
Page 7 of 30 The Journal of Organic Chemistry

1
2
3 Entry R1 R2 Product Yieldb (%)
4
5
6
1 H 4-OMe 4a 87
7
8 2 H 4-Me 4b 93
9
10 3 H 4-Cl 4c 88
11
12 4 H 4-Br 4d 86
13
14
15
5 H 3,5-dimethyl 4e 92
16
17 6 Me H 4f 87
18
19 7 Me 4-Me 4g 90
20
21 8 Me 4-OMe 4h 89
22
23
24
9 Me 4-Cl 4i 83
25
26 10 Me 4-Br 4j 81
27
28 11 Me 4-NO2 4k 79
29
30 12 Me 3-Me 4l 91
31
32
33
13 Me 3,5-dimethyl 4m 90
34
35 14 OMe H 4n 88
36
37 15 OMe 4-Me 4o 93
38
39 16 OMe 4-OMe 4p 90
40
41
42
17 OMe 4-Cl 4q 86
43
44 18 OMe 3-Me 4r 91
45
46 19 OMe 3,5-dimethyl 4s 92
47
48 20 Cl 4-Me 4t 87
49
50
51
21 Cl 4-OMe 4u 85
52
53 22 CO2Me H 4v 79
54
a
55 General conditions: 1 (0.3 mmol), 2 (0.3 mmol), 3 (0.9 mmol), Pd(OAc)2 (5 mol%),
56
57
K2CO3 (1.2 mmol) in CH3CN (2 mL), refluxed (heating at 90 oC) for 12 h. bIsolated
58 yield.
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 8 of 30

1
2
3
4 In subsequent investigation on the substrate scope, the reactions employing
5
6 benzoyl chlorides containing ortho- and meta-substitutent which resulted in the
7
8
9 presence of two different ortho-C-H bonds were then performed. As expected, the
10
11 steric effect produced by the substituent induced the reaction to selectively give single
12
13
14 C-H arylated products 5. As outlined in Table 3, benzoyl chlorides with ortho- or
15
16 meta-methyl group reacted with iodobenzenes containing alkyl, alkoxyl, halogen and
17
18
19 nitro substitution to provide products 5 all with excellent yield via the direct
20
21 three-component operation.
22
23
24 Table 3 Scope of the one-pot single C-H arylationa,b
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
a
51 General conditions: 1a (0.3 mmol), 2 (0.3 mmol), 3 (0.45 mmol), Pd(OAc)2 (5
52
mol%), K2CO3 (1.2 mmol) in CH3CN (2 mL), refluxed (heating at 90 oC) for 12 h.
53
b
54 Isolated yield.
55
56
57
58
59
60
ACS Paragon Plus Environment
Page 9 of 30 The Journal of Organic Chemistry

1
2
3
4 The synthesis of all products 4 and 5 clearly defined the general applicability of
5
6 the OAP in assisting the benzamide ortho-C-H arylation reaction as DG. However,
7
8
9 besides revealing the utility of this useful new DG, another notable advantage of the
10
11 present work was the simple operation by directly subjecting three reactants. To
12
13
14 verify the other important feature of the three-component reaction in generating
15
16 product diversity, the synthesis to products of type 4 by using different
17
18
19 o-aminophenols were then run under the standard reaction conditions. Delightfully,
20
21 the brief examination on the reactions afforded the expected products 4w-4z with also
22
23
24 excellent yields (Scheme 1). Whilst providing the rapid synthetic route to diverse
25
26 products, the successfully execution of these three-component reactions also
27
28
29 demonstrated their potential application in rapidly screening the efficient DG via
30
31 simple variation in the substructure of the DG precursors.
32
33
34
35
36
37
38
39
40
41
42
43
44 Scheme 1 Brief scope of o-aminophenols in the C-H arylation
45
46
47
48 To demonstrate the function of the hydroxyl group in OAP, a control experiment
49
50 employing aniline as alternative amine substrate to reaction with benozyl chloride and
51
52
53 iodobenzene was conducted under the standard condition. No expect C-H arylated
54
55 product was observed in this experiment (Eq 1), implying that the hydroxyl group in
56
57
58 OAP was indispensable for the Pd-catalyzed reaction by acting as chelating site. In
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 10 of 30

1
2
3
4 addition, the KIE experiment employing equal amount of 2a and 2a-d5 to react with
5
6 1a and 3a provided the product 4a and corresponding deuterium labelled product
7
8
9 4a-d3, with the ratio of 4.3 :1 (Eq 2), suggesting that C-H arylation might be a rate
10
11 determining step.
12
13
14
H O standard
15
condition
16 Cl NH2 I no C-H arylation (1)
17
18 H
19
20 D
D O
21 O D D
22 D standard
Cl condition (2)
1a Cl
23 4a
24 3a D D
25 D MeO O OAP OMe
26 2a 2a-d5 4a-d3
27 0.15 mmol 0.15 mmol 4a/4a-d3 = 4.3
28
29
30
In term of the reaction mechanism, the bidentate feature of OAP indicates that
31
32
33 the C-H activation process takes place through similar states as those ones in the
34
35
36
directed arylation using analogous bidentate DG.6d As depicted in Scheme 2, the first
37
38 step of the three-component reaction is the base promoted formation of benzamide 6
39
40
41
from benzoyl chloride and o-aminophenol. The Pd(OAc)2 then incorporates 6 to give
42
43 Pd complex A with the assistance of K2CO3 wherein the ligand may be OAc-, the
44
45
46 reaction medium or the heteroatom in substrate, and A can be further converted to
47
48 complex B via the intramolecular C-H palladation. The oxidative addition of aryl
49
50
51 iodide to B leads to the formation of another Pd complex C which undergoes
52
53 subsequent reductive elimination to form o-arylated Pd species D. The decomposition
54
55
56 of D to the Pd(II) catalyst allows the next round C-H arylation process and give
57
58 simultaneously the single arylated product 5. When another reactive C-H bond
59
60
ACS Paragon Plus Environment
Page 11 of 30 The Journal of Organic Chemistry

1
2
3
4 presents, the double arylated product 4 can be afforded via the repeated catalytic
5
6 cycle.
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Scheme 2 The plausible reaction mechanism
35
36
37
38 CONCLUSION
39
40
41 In conclusion, we have identified o-aminophenol as a highly efficient DG precursor
42
43 enabling the directed ortho-C-H arylation of in situ generated benzamides in
44
45
46 straightforward three-component reactions of benzoyl chlorides, o-aminophenols and
47
48
aryl iodides. The present work discloses not only the low cost and simple OAP as a
49
50
51 practical new bidentate DG, but also the step efficient three-component one-pot C-H
52
53
activation protocol in the synthesis of highly diversified products.
54
55
56
57 EXPERIMENTAL SECTION
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 12 of 30

1
2
3
General information
4
5
6
All chemicals and solvents used in the experiments were obtained from commercial
7
8
9 sources and used directly without further treatment. The 1H and 13
C NMR were
10
11
recorded in 400 MHz apparatus using CDCl3 or DMSO-d6 as solvent. The frequencies
12
13
14 for 1H NMR and 13
C NMR test are 400 MHz and 100 MHz, respectively. The
15
16
chemical shifts were reported in ppm using TMS as internal standard. HRMS results
17
18
19 were tested under ESI model in an MS spectrometer equipped with TOF analyzer.
20
21
22
The melting points were tested in a X-4A instrument without correcting temperature.
23
24
25
General procedure for the synthesis of benzamides 4 and 5
26
27
28
In a 25 mL round bottom flask equipped with a condenser were located
29
30 o-aminophenol 1 (0.3 mmol), acyl chloride 2 (0.3 mmol), iodobenzene 3 (0.9 mmol in
31
32
33
the synthesis of 4)/(0.45 mmol in the synthesis of 5), Pd(OAc)2 (0.015 mmol), K2CO3
34
35 (1.2 mmol) and CH3CN (2 mL). The mixture was refluxed at 82 oC (external heating
36
37
38 at 90 oC) for 12 h. Upon completion (TCL), the vessel was allowed to cool down to
39
40 room temperature, and 10 mL water was added. The heterogeneous mixture was
41
42
43 extracted with ethyl acetate (3 ×10 mL). The combined organic phase was dried over
44
45 Na2SO4. After filtration, the acquired solution was collected and the solvent was
46
47
48 removed at reduced pressure. The residue was subjected to silica gel column
49
50 chromatography to give pure products by using mixed petroleum ether and ethyl
51
52
53 acetate (VPET: VEA = 10:1).
54
55
56
57
58
59
60
ACS Paragon Plus Environment
Page 13 of 30 The Journal of Organic Chemistry

1
2
3
4 N-(2-Hydroxyphenyl)-2,6-di(p-methoxyphenyl) benzamide (4a). Yield: 87%, 111
5
6 o 1
mg; white solid; mp 217-219 C; Rf = 0.25; H NMR (400 MHz, DMSO-d6): δ = 9.51
7
8
9 (s, 1 H), 9.28 (s, 1 H), 7.54 (t, J = 7.6 Hz, 1 H), 7.45 (d, J = 8.0 Hz, 4 H), 7.35 (d, J =
10
11 7.6 Hz, 2 H), 7.06 (d, J = 7.6 Hz, 1 H), 6.93 (d, J = 8.0 Hz, 5 H), 6.75 (d, J = 7.6 Hz, 1
12
13 13
14 H), 6.65 (t, J = 7.6 Hz, 1 H), 3.74 (s, 6 H); C NMR (100 MHz, DMSO-d6): δ =
15
16 168.2, 159.2, 149.1, 139.8, 136.1, 133.0, 130.2, 129.4, 129.0, 125.8, 123.3, 119.3,
17
18
19 116.8, 114.1, 55.6; ESI-HRMS Calcd for C27H24NO4 [M + H]+ 426.1700, found
20
21 426.1704.
22
23
24
25 N-(2-Hydroxyphenyl)-2,6-ditolyl benzamide (4b). Yield: 93%, 110 mg; white solid;
26
27 mp 206-208 oC; Rf = 0.43; 1H NMR (400 MHz, CDCl3): δ = 7.88 (s, 1 H), 7.55 (t, J =
28
29
30 7.6 Hz, 1 H), 7.43 (d, J = 8.0 Hz, 2 H), 7.38 (d, J = 7.6 Hz, 4 H), 7.23 (d, J = 7.6 Hz, 4
31
32 H), 7.08 (s, 1 H), 7.05 (t, J = 7.8 Hz, 1 H), 6.93 (d, J = 8.4 Hz, 1 H), 6.63 (t, J = 7.4
33
34
35 Hz, 1 H), 5.80 (d, J = 8.0 Hz, 1 H), 2.39 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ =
36
37 169.9, 149.7, 141.0, 137.7, 137.1, 133.7, 130.1, 129.5, 129.3, 128.4, 127.5, 125.5,
38
39
40 122.2, 120.1, 119.8, 21.2; ESI-HRMS Calcd for C27H24NO2 [M + H]+ 394.1802,
41
42 found 394.1808.
43
44
45
46 N-(2-Hydroxyphenyl)-2,6-di(p-chlorophenyl) benzamide (4c). Yield: 88%, 114 mg;
47
48 white solid; mp 253-255 oC; Rf = 0.18; 1H NMR (400 MHz, DMSO-d6): δ = 9.62 (s, 1
49
50
51 H), 9.30 (s, 1 H), 7.61 (t, J = 7.6 Hz, 1 H), 7.55 (d, J = 8.4 Hz, 4 H), 7.45-7.43 (m, 6
52
53 H), 7.00 (d, J = 8.0 Hz, 1 H), 6.92 (t, J = 7.8 Hz, 1 H), 6.76 (d, J = 8.4 Hz, 1 H), 6.65
54
55
56 (t, J = 7.6 Hz, 1 H); 13C NMR (100 MHz, DMSO-d6): δ = 167.4, 149.7, 139.4, 138.8,
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 14 of 30

1
2
3
4 136.4, 132.8, 130.9, 129.6, 128.6, 126.2, 125.6, 124.1, 119.2, 116.5; ESI-HRMS
5
6 Calcd for C25H17Cl2KNO2 [M + K]+ 472.0268, found 472.0287.
7
8
9
10 N-(2-Hydroxyphenyl)-2,6-di(p-bromophenyl) benzamide (4d). Yield: 86%, 134 mg;
11
12 white solid; mp 278-280 oC; Rf = 0.22; 1H NMR (400 MHz, DMSO-d6): δ = 9.67 (s, 1
13
14
15 H), 9.36 (s, 1 H), 7.63-7.57 (m, 5 H), 7.49 (d, J = 8.4 Hz, 4 H), 7.44 (d, J = 8.0 Hz, 2
16
17 H), 7.00 (d, J = 7.6 Hz, 1 H), 6.92 (t, J = 7.6 Hz, 1 H), 6.77 (d, J = 8.0 Hz, 1 H), 6.66
18
19
20 (t, J = 7.6 Hz, 1 H); 13C NMR (100 MHz, DMSO-d6): δ = 167.4, 149.7, 139.7, 138.8,
21
22 136.2, 131.5, 131.3, 129.7, 129.6, 126.2, 125.6, 124.1, 121.4, 119.2, 116.5;
23
24
25 ESI-HRMS Calcd for C25H17Br2NNaO2 [M + Na]+ 543.9518, found 543.9525.
26
27
28 N-(2-Hydroxyphenyl)-2,6-di(3,5-dimethylphenyl) benzamide (4e). Yield: 92%, 116
29
30
mg; white solid; mp 234-236 oC; Rf = 0.37; 1H NMR (400 MHz, CDCl3): δ = 7.64 (s,
31
32
33 1 H), 7.54 (t, J = 7.6 Hz, 1 H), 7.43 (d, J = 7.6 Hz, 2 H), 7.10 (s, 5 H), 7.06 (s, 1 H),
34
35
36
7.03 (s, 2 H), 6.93 (d, J = 8.4 Hz, 1 H), 6.67 (t, J = 7.4 Hz, 1 H), 5.87 (d, J = 7.6 Hz, 1
37
13
38 H), 2.31 (s, 12 H); C NMR (100 MHz, CDCl3): δ = 170.0, 150.1, 141.2, 140.0,
39
40
41
138.4, 133.6, 130.0, 129.5, 129.2, 127.5, 126.3, 125.4, 122.4, 120.0, 119.9, 21.3;
42
43 ESI-HRMS Calcd for C29H27NNaO2 [M + Na]+ 444.1934, found 444.1921.
44
45
46 N-(2-Hydroxyphenyl)-2,6-diphenyl 4-methylbenzamide (4f). Yield: 87%, 99 mg;
47
48
49 white solid; mp 269-271 oC; Rf = 0.50; 1H NMR (400 MHz, CDCl3): δ = 7.81 (s, 1 H),
50
51 7.48 (d, J = 7.2 Hz, 4 H), 7.45-7.39 (m, 6 H), 7.29 (s, 2 H), 7.07 (s, 1 H), 7.03 (t, J =
52
53
54 7.8 Hz, 1 H), 6.91 (d, J = 8.0 Hz, 1 H), 6.62 (t, J = 7.4 Hz, 1 H), 5.74 (d, J = 8.0 Hz, 1
55
56
H), 2.49 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 169.8, 149.7, 141.1, 140.3, 140.2,
57
58
59
60
ACS Paragon Plus Environment
Page 15 of 30 The Journal of Organic Chemistry

1
2
3
4 131.1, 130.2, 128.8, 128.5, 127.9, 127.5, 125.4, 122.2, 120.1, 119.9, 21.4; ESI-HRMS
5
6 Calcd for C26H22NO2 [M + H]+ 380.1645, found 380.1638.
7
8
9
10 N-(2-Hydroxyphenyl)-2,6-ditolyl 4-methylbenzamide (4g). Yield: 90%, 110 mg;
11
12 white solid; mp 221-223 oC; Rf = 0.45; 1H NMR (400 MHz, CDCl3): δ = 8.01 (s, 1 H),
13
14
15 7.36 (d, J = 7.6 Hz, 4 H), 7.23 (t, J = 8.2 Hz, 6 H), 7.07 (s, 1 H), 7.04 (t, J = 7.8 Hz, 1
16
17 H), 6.92 (d, J = 8.0 Hz, 1 H), 6.62 (t, J = 7.4 Hz, 1 H), 5.75 (d, J = 8.0 Hz, 1 H), 2.46
18
19
20 (s, 3 H), 2.38 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ = 170.1, 149.7, 141.1, 140.2,
21
22 137.6, 137.3, 130.9, 130.1, 129.5, 128.3, 127.4, 125.6, 122.2, 120.0, 119.9, 21.4, 21.2;
23
24
25 ESI-HRMS Calcd for C28H26NO2 [M + H]+ 408.1958, found 408.1959.
26
27
28 N-(2-Hydroxyphenyl)-2,6-di(p-methoxylphenyl) 4-methylbenzamide (4h). Yield:
29
30
89%, 117 mg; white solid; mp 243-245 oC; Rf = 0.15; 1H NMR (400 MHz, DMSO-d6):
31
32
33 δ = 9.37 (s, 1 H), 9.29 (s, 1 H), 7.44 (d, J = 8.4 Hz, 4 H), 7.17 (s, 2 H), 7.06 (d, J = 8.0
34
35
36
Hz, 1 H), 6.93-6.88 (m, 5 H), 6.74 (d, J = 8.0 Hz, 1 H), 6.65 (t, J = 7.8 Hz, 1 H), 3.74
37
13
38 (s, 6 H), 2.41 (s, 3 H); C NMR (100 MHz, DMSO-d6): δ = 168.5, 159.0, 149.0,
39
40
41
139.7, 138.8, 133.4, 133.1, 130.2, 129.6, 126.3, 125.8, 123.2, 119.3, 116.8, 114.0,
42
43 55.5, 21.2; ESI-HRMS Calcd for C28H26NO4 [M + H]+ 440.1856, found 440.1865.
44
45
46 N-(2-Hydroxyphenyl)-2,6-di(p-chlorophenyl) 4-methylbenzamide (4i). Yield: 83%,
47
48
49 111 mg; white solid; mp 256-258 oC; Rf = 0.45; 1H NMR (400 MHz, DMSO-d6): δ =
50
51 9.55 (s, 1 H), 9.33 (s, 1 H), 7.53 (d, J = 8.0 Hz, 4 H), 7.43 (d, J = 8.4 Hz, 4 H), 7.26
52
53
54 (s, 2 H), 7.01 (d, J = 7.6 Hz, 1 H), 6.91 (t, J = 7.6 Hz, 1 H), 6.76 (d, J = 8.0 Hz, 1 H),
55
56
6.65 (t, J = 7.6 Hz, 1 H), 2.43 (s, 3 H); 13C NMR (100 MHz, DMSO-d6): δ = 167.6,
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 16 of 30

1
2
3
4 149.5, 139.5, 139.2, 138.8, 133.7, 132.7, 130.9, 130.1, 128.5, 126.1, 125.8, 123.8,
5
6 119.2, 116.6, 21.2; ESI-HRMS Calcd for C26H20Cl2NO2 [M + H]+ 448.0866, found
7
8
9 448.0883.
10
11
12 N-(2-Hydroxyphenyl)-2,6-di(p-bromophenyl) 4-methylbenzamide (4j). Yield: 81%,
13
14
15 130 mg; white solid; mp 277-279 oC; Rf = 0.20; 1H NMR (400 MHz, DMSO-d6): δ =
16
17 9.55 (s, 1 H), 9.34 (s, 1 H), 7.57 (d, J = 8.4 Hz, 4 H), 7.47 (d, J = 8.4 Hz, 4 H), 7.26
18
19
20 (s, 2 H), 7.00 (d, J = 7.6 Hz, 1 H), 6.92 (t, J = 7.6 Hz, 1 H), 6.76 (d, J = 8.0 Hz, 1 H),
21
22 6.65 (t, J = 7.6 Hz, 1 H), 2.44 (s, 3 H); 13C NMR (100 MHz, DMSO-d6): δ = 167.6,
23
24
25 149.6, 139.8, 139.2, 138.8, 133.6, 131.5, 131.2, 130.1, 126.1, 125.8, 123.9, 121.4,
26
27 119.2, 116.6, 21.2; ESI-HRMS Calcd for C26H19Br2NNaO2 [M + Na]+ 557.9675,
28
29
30 found 557.9675.
31
32
33 N-(2-Hydroxyphenyl)-2,6-di(p-nitrophenyl) 4-methylbenzamide (4k). Yield: 79%,
34
35
111 mg; white solid; mp 296-298 oC; Rf = 0.12; 1H NMR (400 MHz, DMSO-d6): δ =
36
37
38 9.68 (s, 1 H), 9.39 (s, 1 H), 8.26 (d, J = 8.8 Hz, 4 H), 7.82 (d, J = 8.4 Hz, 4 H), 7.40
39
40
41
(s, 2 H), 6.99 (d, J = 8.0 Hz, 1 H), 6.90 (t, J = 7.6 Hz, 1 H), 6.75 (d, J = 8.0 Hz, 1 H),
42
43 6.63 (t, J = 7.6 Hz, 1 H), 2.48 (s, 3 H); 13C NMR (100 MHz, DMSO-d6): δ = 166.9,
44
45
46 150.1, 147.4, 147.2, 139.6, 138.2, 134.0, 130.8, 130.5, 126.3, 125.3, 124.6, 123.7,
47
48 119.1, 116.2, 21.1; ESI-HRMS Calcd for C26H20N3O6 [M + H]+ 470.1347, found
49
50
51 470.1349.
52
53
54 N-(2-Hydroxyphenyl)-2,6-di(m-methylphenyl) 4-methylbenzamide (4l). Yield: 91%,
55
56
111 mg; white solid; mp 235-237 oC; Rf = 0.33; 1H NMR (400 MHz, CDCl3): δ = 7.81
57
58
59
60
ACS Paragon Plus Environment
Page 17 of 30 The Journal of Organic Chemistry

1
2
3
4 (s, 1 H), 7.33-7.25 (m, 8 H), 7.20 (d, J = 7.2 Hz, 2 H), 7.06-7.02 (m, 2 H), 6.92 (d, J =
5
6 8.4 Hz, 1 H), 6.64 (t, J = 8.0 Hz, 1 H), 5.76 (d, J = 8.0 Hz, 1 H), 2.47 (s, 3 H), 2.36 (s,
7
8 13
9 6 H); C NMR (100 MHz, CDCl3): δ = 170.0, 149.9, 141.2, 140.2, 140.2, 138.5,
10
11 131.0, 130.1, 129.2, 128.7, 128.6, 127.5, 125.5, 122.3, 120.1, 119.9, 21.4; ESI-HRMS
12
13
14 Calcd for C28H26NO2 [M + H]+ 408.1958, found 408.1962.
15
16
17 N-(2-Hydroxyphenyl)-2,6-di(3,5-dimethylphenyl) 4-methylbenzamide (4m). Yield:
18
19 o 1
20 90%, 117 mg; white solid; mp 232-234 C; Rf = 0.65; H NMR (400 MHz, CDCl3): δ =
21
22 7.77 (s, 1 H), 7.25 (s, 2 H), 7.09 (s, 5 H), 7.05 (s, 1 H), 7.01 (s, 2 H), 6.92 (d, J = 8.4
23
24
25 Hz, 1 H), 6.66 (t, J = 7.6 Hz, 1 H), 5,83 (d, J = 8.0 Hz, 1 H), 2.45 (s, 3 H), 2.31 (s, 12
26
27 H); 13C NMR (100 MHz, CDCl3): δ = 170.2, 150.1, 141.2, 140.2, 140.1, 138.4, 130.9,
28
29
30 130.0, 129.4, 127.5, 126.3, 125.6, 122.4, 120.0, 119.9, 21.4, 21.3; ESI-HRMS Calcd
31
32 for C30H29KNO2 [M + K]+ 474.1830, found 474.1804.
33
34
35
36
N-(2-Hydroxyphenyl)-2,6-diphenyl 4-methoxylbenzamide (4n). Yield: 88%, 104 mg;
37
38 white solid; mp 233-235 oC; Rf = 0.15; 1H NMR (400 MHz, CDCl3): δ = 7.89 (s, 1 H),
39
40
41
7.49-7.40 (m, 10 H), 7.06 (s, 1 H), 7.02 (d, J = 8.4 Hz, 1 H), 6.97 (s, 2 H), 6.90 (d, J =
42
43 8.0 Hz, 1 H), 6.61 (t, J = 7.6 Hz, 1 H), 5.68 (d, J = 8.0 Hz, 1 H), 3.90 (s, 3 H); 13C
44
45
46 NMR (100 MHz, CDCl3): δ = 169.6, 160.3, 149.8, 143.0, 140.1, 128.8, 128.4, 128.1,
47
48 127.5, 126.6, 125.5, 122.2, 120.1, 119.9, 114.9, 55.6; ESI-HRMS Calcd for
49
50
51 C26H22NO3 [M + H]+ 396.1594, found 396.1599.
52
53
54 N-(2-Hydroxyphenyl)-2,6-ditolyl 4-methoxylbenzamide (4o). Yield: 93%, 118 mg;
55
56
white solid; mp 230-232 oC; Rf = 0.20; 1H NMR (400 MHz, CDCl3): δ = 8.07 (s, 1 H),
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 18 of 30

1
2
3
4 7.32 (d, J = 8.0 Hz, 4 H), 7.20 (d, J = 8.0 Hz, 4 H), 7.12 (s, 1 H), 7.02 (t, J = 7.6 Hz, 1
5
6 H), 6.92-6.89 (m, 3 H), 6.59 (t, J = 7.6 Hz, 1 H), 5.71 (d, J = 7.6 Hz, 1 H), 3.86 (s, 3
7
8
9 H), 2.37 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ = 170.0, 160.2, 149.7, 143.0, 137.8,
10
11 137.3, 129.5, 128.2, 127.4, 126.5, 125.7, 122.2, 120.0, 119.8, 114.7, 55.6, 21.2;
12
13
14 ESI-HRMS Calcd for C28H26NO3 [M + H]+ 424.1907, found 424.1903.
15
16
17 N-(2-Hydroxyphenyl)-2,6-di(p-methoxylphenyl) 4-methoxylbenzamide (4p). Yield:
18
19 o 1
20 90%, 123 mg; white solid; mp 212-214 C; Rf = 0.11; H NMR (400 MHz, CDCl3): δ =
21
22 8.07 (brs, 1 H), 7.35 (d, J = 8.4 Hz, 4 H), 7.20 (s, 1 H), 7.02 (t, J = 7.8 Hz, 1 H),
23
24
25 6.92-6.89 (m, 7 H), 6.62 (t, J = 7.6 Hz, 1 H), 5.86 (d, J = 8.0 Hz, 1 H), 3.87 (s, 3 H),
26
27 13
3.80 (s, 6 H); C NMR (100 MHz, CDCl3): δ = 170.1, 160.1, 159.5, 149.6, 142.6,
28
29
30 132.4, 129.5, 127.4, 126.5, 125.7, 122.3, 120.1, 119.7, 114.6, 114.2, 55.6, 55.4;
31
32 ESI-HRMS Calcd for C28H25KNO5 [M + K]+ 494.1364, found 494.1385.
33
34
35
36
N-(2-Hydroxyphenyl)-2,6-di(p-chlorophenyl) 4-methoxylbenzamide (4q). Yield:
37
38 86%, 119 mg; white solid; mp 166-168 oC; Rf = 0.45; 1H NMR (400 MHz, DMSO-d6):
39
40
41
δ = 9.47 (s, 1 H), 9.31 (s, 1 H), 7.52 (d, J = 8.0 Hz, 4 H), 7.40 (d, J = 8.0 Hz, 4 H),
42
43 6.96-6.94 (m, 3 H), 6.87 (t, J = 7.4 Hz, 1 H), 6.72 (d, J = 8.0 Hz, 1 H), 6.61 (t, J = 7.4
44
45 13
46 Hz, 1 H), 3.84 (s, 3 H); C NMR (100 MHz, DMSO-d6): δ = 167.1, 159.0, 149.0,
47
48 140.1, 138.8, 132.4, 130.3, 128.7, 128.1, 125.6, 125.4, 123.3, 118.7, 116.0, 114.4,
49
50
51 55.5; ESI-HRMS Calcd for C26H20Cl2NO3 [M + H]+ 464.0815, found 464.0817.
52
53
54 N-(2-Hydroxyphenyl)-2,6-di(m-methylphenyl) 4-methoxylbenzamide (4r). Yield:
55
56
91%, 115 mg; white solid; mp 177-179 oC; Rf = 0.28; 1H NMR (400 MHz, CDCl3): δ =
57
58
59
60
ACS Paragon Plus Environment
Page 19 of 30 The Journal of Organic Chemistry

1
2
3
4 7.88 (s, 1 H), 7.32-7.24 (m, 6 H), 7.20 (d, J = 7.2 Hz, 2 H), 7.09 (s, 1 H), 7.02 (t, J =
5
6 7.8 Hz, 1 H), 6.95 (s, 2 H), 6.89 (d, J = 7.6 Hz, 1 H), 6.62 (t, J = 7.6 Hz, 1 H), 5.75 (d,
7
8
9 J = 8.0 Hz, 1 H), 3.89 (s, 3 H), 2.35 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ = 169.3,
10
11 159.7, 149.4, 142.6, 139.6, 138.1, 128.6, 128.3, 128.2, 127.0, 126.0, 125.1, 124.9,
12
13
14 121.8, 119.5, 119.3, 114.3, 55.1, 20.9; ESI-HRMS Calcd for C28H26NO3 [M + H]+
15
16 424.1907, found 424.1910.
17
18
19
20 N-(2-Hydroxyphenyl)-2,6-di(3,5-dimethylphenyl) 4-methoxylbenzamide (4s).
21
22 Yield: 92%, 124 mg; white solid; mp 220-222 oC; Rf = 0.62; 1H NMR (400 MHz,
23
24
25 CDCl3): δ = 7.83 (s, 1 H), 7.09 (s, 4 H), 7.06 (s, 1 H), 7.03 (s, 3 H), 6.94-6.91 (m, 3
26
27 H), 6.65 (t, J = 7.6 Hz, 1 H), 5.79 (d, J = 7.6 Hz, 1 H), 3.89 (s, 3 H), 2.31 (s, 12 H);
28
29 13
30 C NMR (100 MHz, CDCl3): δ = 170.0, 160.1, 150.1, 143.2, 140.1, 138.5, 129.6,
31
32 127.4, 126.4, 126.2, 125.6, 122.3, 120.0, 119.9, 114.6, 55.6, 21.3; ESI-HRMS Calcd
33
34
35 for C30H30NO3 [M + H]+ 452.2220, found 452.2236.
36
37
38 N-(2-Hydroxyphenyl)-2,6-ditolyl 4-chlorobenzamide (4t). Yield: 87%, 111 mg; white
39
40
41
solid; mp 240-242 oC; Rf = 0.58; 1H NMR (400 MHz, DMSO-d6): δ = 9.60 (s, 1 H),
42
43 9.36 (s, 1 H), 7.46-7.42 (m, 6 H), 7.18 (d, J = 8.0 Hz, 4 H), 7.09 (d, J = 7.2 Hz, 1 H),
44
45
46 6.89 (t, J = 7.6 Hz, 1 H), 6.75 (d, J = 8.4 Hz, 1 H), 6.63 (t, J = 7.6 Hz, 1 H), 2.29 (s, 6
47
13
48 H); C NMR (100 MHz, DMSO-d6): δ = 167.0, 149.2, 142.0, 137.6, 136.5, 135.2,
49
50
51 133.6, 129.3, 128.9, 128.5, 125.9, 123.6, 119.2, 116.4, 21.2; ESI-HRMS Calcd for
52
53 C27H23ClNO2 [M + H]+ 428.1412, found 428.1416.
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 20 of 30

1
2
3
4 N-(2-Hydroxyphenyl)-2,6-di(p-methoxylphenyl) 4-chlorobenzamide (4u). Yield:
5
6 o 1
85%, 117 mg; white solid; mp 230-232 C; Rf = 0.15; H NMR (400 MHz, CDCl3): δ =
7
8
9 7.71 (s, 1 H), 7.38-7.34 (m, 6 H), 7.24 (s, 1 H), 7.04 (t, J = 7.8 Hz, 1 H), 6.93-6.89 (m,
10
11 5 H), 6.64 (t, J = 7.6 Hz, 1 H), 5.98 (d, J = 7.6 Hz, 1 H), 3.80 (s, 6 H); 13C NMR (100
12
13
14 MHz, CDCl3): δ = 168.6, 159.3, 148.9, 141.8, 135.2, 131.6, 130.5, 129.0, 128.4,
15
16 127.1, 124.8, 121.8, 119.8, 119.2, 113.8, 54.9; ESI-HRMS Calcd for C27H23ClNO4
17
18
19 [M + H]+ 460.1310, found 460.1312.
20
21
22 N-(2-Hydroxyphenyl)-2,6-diphenyl 4-(methoxycarbonyl)benzamide (4v). Yield
23
24
25 79%, 100 mg; pale yellow solid; mp 211-213 oC; Rf = 0.14; 1H NMR (400 MHz,
26
27 CDCl3): δ 8.11 (s, 2 H), 7.48-7.41 (m, 11 H), 7.28 (d, J = 6.4 Hz, 1 H), 7.03 (t, J = 7.6
28
29
30 Hz, 1 H), 6.88 (d, J = 8.4 Hz, 1 H), 6.63 (t, J = 7.6 Hz, 1 H), 5.92 (d, J = 8.0 Hz, 1 H),
31
32 3.95 (s, 3 H); 13C NMR (100 MHz, CDCl3): 168.6, 166.1, 149.5, 141.4, 139.0, 137.6,
33
34
35 131.5, 130.3, 128.9, 128.5, 128.4, 127.7, 125.1, 122.4, 120.4, 119.7, 52.6; ESI-HRMS
36
37 Calcd for C27H22NO4 [M + H]+ 4241543, found 424.1542.
38
39
40
41
N-(2-Hydroxy-4-methylphenyl)-2,6-diphenyl benzamide (4w). Yield: 84%, 96 mg;
42
43 white solid; mp 275-277 oC; Rf = 0.35; 1H NMR (400 MHz, CDCl3): δ = 7.62 (s, 1 H),
44
45
46 7.59-7.55 (m, 1 H), 7.49-7.47 (m, 5 H), 7.45-7.42 (m, 4 H), 7.40-7.38 (m, 3 H), 7.02
47
48 (s, 1 H), 6.71 (s, 1 H), 6.42 (d, J = 8.4 Hz, 1 H), 5.68 (d, J = 7.6 Hz, 1 H), 2.20 (s, 3
49
50
51 H); 13C NMR (100 MHz, CDCl3): δ = 169.4, 149.4, 141.0, 140.0, 137.8, 133.9, 130.1,
52
53 129.5, 128.8, 128.5, 128.0, 122.7, 122.0, 121.0, 120.3, 20.9; ESI-HRMS Calcd for
54
55
56 C26H21KNO2 [M + K]+ 418.1204, found 418.1185.
57
58
59
60
ACS Paragon Plus Environment
Page 21 of 30 The Journal of Organic Chemistry

1
2
3
4 N-(2-Hydroxy-4-methylphenyl)-2,6-ditolyl benzamide (4x). Yield: 93%, 114 mg;
5
6 o 1
white solid; mp 230-232 C; Rf = 0.50; H NMR (400 MHz, CDCl3): δ = 7.78 (s, 1 H),
7
8
9 7.51 (t, J = 7.6 Hz, 1 H), 7.39 (d, J = 7.6 Hz, 2 H), 7.33 (d, J = 8.0 Hz, 4 H), 7.18 (d, J
10
11 = 8.0 Hz, 4 H), 7.08 (s, 1 H), 6.69 (s, 1 H), 6.41 (d, J = 8.0 Hz, 1 H), 5.73 (d, J = 8.0
12
13
14 Hz, 1 H), 2.36 (s, 6 H), 2.19 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 169.7, 149.3,
15
16 141.0, 137.7, 137.6, 137.2, 133.8, 130.0, 129.5, 129.3, 128.4, 123.0, 122.1, 120.9,
17
18
19 120.1, 21.2, 20.9; ESI-HRMS Calcd for C28H26NO2 [M + H]+ 408.1958, found
20
21 408.1961.
22
23
24
25 N-(2-Hydroxy-4-chlorophenyl)-2,6-ditolyl benzamide (4y). Yield: 92%, 118 mg;
26
27 white solid; mp 166-168 oC; Rf = 0.25; 1H NMR (400 MHz, DMSO-d6): δ = 9.84 (s, 1
28
29
30 H), 9.45 (s, 1 H), 7.55 (t, J = 7.6 Hz, 1 H), 7.41-7.35 (m, 6 H), 7.17-7.12 (m, 5 H),
31
32 13
6.77 (s, 1 H), 6.71 (d, J = 8.8 Hz, 1 H), 2.30 (s, 6 H); C NMR (100 MHz,
33
34
35 DMSO-d6): δ = 168.0, 150.1, 139.9, 137.8, 137.0, 136.0, 129.4, 129.2, 129.2, 129.0,
36
37 128.9, 125.3, 124.4, 119.0, 116.1, 21.2; ESI-HRMS Calcd for C27H23ClNO2 [M + H]+
38
39
40 428.1412, found 428.1412.
41
42
43 N-(2-Hydroxy-4-chlorophenyl)-2,6-di(p-chlorophenyl) benzamide (4z). Yield: 90%,
44
45 o 1
46 126 mg; hite solid; mp 215-217 C; Rf = 0.13; H NMR (400 MHz, DMSO-d6): δ =
47
48 10.02 (brs, 1 H), 9.66 (s, 1 H), 7.59 (t, J = 7.6 Hz, 1 H), 7.53 (d, J = 7.6 Hz, 4 H), 7.43
49
50
51 (d, J = 6.8 Hz, 6 H), 7.11 (d, J = 8.4 Hz, 1 H), 6.78 (s, 1 H), 6.72 (d, J = 8.4 Hz, 1 H);
52
53 13
C NMR (100 MHz, DMSO-d6): δ = 166.9, 150.2, 138.8, 138.2, 135.8, 132.3, 130.4,
54
55
56 129.1, 129.1, 128.8, 128.1, 124.6, 124.3, 118.4, 115.3; ESI-HRMS Calcd for
57
58 C25H17Cl3NO2 [M + H]+ 468.0319, found 468.0313.
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 22 of 30

1
2
3
4 N-(2-Hydroxyphenyl)-2-methyl-6-phenyl benzamide (5a). Yield: 90%, 82 mg; white
5
6 solid; mp 135-137 oC; Rf = 0.33; 1H NMR (400 MHz, CDCl3): δ = 8.51 (s, 1 H),
7
8
9 7.40-7.30 (m, 7 H), 7.24 (d, J = 7.2 Hz, 2 H), 7.01 (t, J = 7.8 Hz, 1 H), 6.87 (d, J = 8.0
10
11 Hz, 1 H), 6.65 (t, J = 7.6 Hz, 1 H), 6.25 (d, J = 7.6 Hz, 1 H), 2.45 (s, 3 H); 13C NMR
12
13
14 (100 MHz, CDCl3): δ = 170.1, 148.9, 140.0, 139.8, 136.5, 134.5, 130.0, 129.8, 128.9,
15
16 128.5, 127.9, 127.6, 127.3, 125.4, 122.2, 120.4, 119.4, 19.9; ESI-HRMS Calcd for
17
18
19 C20H18NO2 [M + H]+ 304.1332, found 304.1332.
20
21
22 N-(2-Hydroxyphenyl)-2-methyl-6-(tolyl) benzamide (5b). Yield: 95%, 90 mg; white
23
24
25 solid; mp 164-166 oC; Rf = 0.25; 1H NMR (400 MHz, CDCl3): δ = 8.59 (s, 1 H), 7.43
26
27 (s, 1 H), 7.35 (t, J = 7.6 Hz, 1 H), 7.27 (d, J = 8.0 Hz, 2 H), 7.21 (t, J = 9.0 Hz, 2 H),
28
29
30 7.12 (d, J = 8.0 Hz, 2 H), 6.99 (t, J = 7.6 Hz, 1 H), 6.85 (d, J = 8.0 Hz, 1 H), 6.65 (t, J
31
32 = 7.6 Hz, 1 H), 6.34 (d, J = 7.6 Hz, 1 H), 2.42 (s, 3 H), 2.31 (s, 3 H); 13C NMR (100
33
34
35 MHz, CDCl3): δ = 170.3, 148.8, 139.8, 137.7, 137.1, 136.3, 134.6, 129.9, 129.5,
36
37 128.4, 127.6, 127.2, 125.6, 122.2, 120.3, 119.3, 21.1, 19.8; ESI-HRMS Calcd for
38
39
40 C21H20NO2 [M + H]+ 318.1489, found 318.1491.
41
42
43 N-(2-Hydroxyphenyl)-2-methyl-6-(p-methoxylphenyl) benzamide (5c). Yield: 92%,
44
45 o 1
46 92 mg; white solid; mp 136-138 C; Rf = 0.80; H NMR (400 MHz, CDCl3): δ = 8.61
47
48 (s, 1 H), 7.39-7.31 (m, 4 H), 7.23 (t, J = 7.4 Hz, 2 H), 7.04 (t, J = 7.8 Hz, 1 H),
49
50
51 6.92-6.87 (m, 3 H), 6.68 (t, J = 7.6 Hz, 1 H), 6.30 (d, J = 7.2 Hz, 1 H), 3.76 (s, 3 H),
52
53 13
2.46 (s, 3 H); C NMR (100 MHz, CDCl3): δ = 170.4, 159.4, 148.9, 139.4, 136.4,
54
55
56 134.4, 132.2, 130.0, 129.7, 129.4, 127.5, 127.3, 125.5, 122.2, 120.3, 119.5, 114.3,
57
58 55.4, 19.9; ESI-HRMS Calcd for C21H20NO3 [M + H]+ 334.1438, found 334.1442.
59
60
ACS Paragon Plus Environment
Page 23 of 30 The Journal of Organic Chemistry

1
2
3
4 N-(2-Hydroxyphenyl)-2-methyl-6-(p-chlorophenyl) benzamide (5d). Yield: 88%, 89
5
6 o 1
mg; white solid; mp 162-164 C; Rf = 0.20; H NMR (400 MHz, CDCl3): δ = 8.41
7
8
9 (brs, 1 H), 7.50 (s, 1 H), 7.39 (t, J = 7.6 Hz, 1 H), 7.34-7.28 (m, 4 H), 7.24-7.21 (m, 2
10
11 H), 7.04 (t, J = 7.8 Hz, 1 H), 6.88 (d, J = 8.0 Hz, 1 H), 6.72 (t, J = 7.4 Hz, 1 H), 6.49
12
13
14 (d, J = 8.0 Hz, 1 H), 2.43 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 169.8, 148.6,
15
16 138.5, 138.3, 136.4, 134.6, 134.0, 130.0, 130.0, 129.8, 128.9, 127.4, 127.3, 125.3,
17
18
19 121.9, 120.6, 119.2, 19.7; ESI-HRMS Calcd for C20H17ClNO2 [M + H]+ 338.0942,
20
21 found 338.0944.
22
23
24
25 N-(2-Hydroxyphenyl)-2-methyl-6-(p-nitrophenyl) benzamide (5e). Yield: 86%, 90
26
27 mg; white solid; mp 171-173 oC; Rf = 0.1; 1H NMR (400 MHz, DMSO-d6): δ = 9.73
28
29
30 (s, 1 H), 9.57 (s, 1 H), 8.24 (d, J = 7.6 Hz, 2 H), 7.78 (d, J = 8.0 Hz, 2 H), 7.46 (t, J =
31
32 7.4 Hz, 1 H), 7.39 (d, J = 7.2 Hz, 1 H), 7.35-7.29 (m, 2 H), 6.98 (t, J = 7.4 Hz, 1 H),
33
34
35 6.84 (d, J = 7.6 Hz, 1 H), 6.74 (t, J = 7.6 Hz, 1 H), 2.45 (s, 3 H); 13C NMR (100 MHz,
36
37 DMSO-d6): δ = 167.3, 149.6, 147.2, 146.6, 137.0, 136.8, 135.0, 130.1, 129.9, 128.9,
38
39
40 127.0, 125.9, 125.1, 124.3, 123.2, 118.8, 116.0, 19.1; ESI-HRMS Calcd for
41
42 C20H16N2NaO4 [M + Na]+ 371.1002, found 371.0984.
43
44
45
46 N-(2-Hydroxyphenyl)-2-methyl-6-(m-methylphenyl) benzamide (5f). Yield: 93%,
47
48 89 mg; white solid; mp 174-176 oC; Rf = 0.29; 1H NMR (400 MHz, CDCl3): δ = 8.51
49
50
51 (s, 1 H), 7.38 (t, J = 7.6 Hz, 1 H), 7.31 (s, 1 H), 7.27-7.18 (m, 5 H), 7.13 (d, J = 7.2
52
53 Hz, 1 H), 7.02 (t, J = 7.6 Hz, 1 H), 6.89 (d, J = 8.0 Hz, 1 H), 6.67 (t, J = 7.4 Hz, 1 H),
54
55
56 6.25 (d, J = 7.6 Hz, 1 H), 2.46 (s, 3 H), 2.28 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ
57
58 = 170.2, 149.1, 140.0, 139.9, 138.6, 136.5, 134.4, 129.9, 129.7, 129.2, 128.8, 128.6,
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 24 of 30

1
2
3
4 127.5, 127.3, 125.6, 125.4, 122.2, 120.3, 119.5, 21.4, 19.9; ESI-HRMS Calcd for
5
6 C21H20NO2 [M + H]+ 318.1489, found 318.1477.
7
8
9
10 N-(2-Hydroxyphenyl)-2-methyl-6-(3,5-dimethylphenyl) benzamide (5g). Yield:
11
12 91%, 90 mg; white solid; mp 184-186 oC; Rf = 0.40; 1H NMR (400 MHz, CDCl3): δ =
13
14
15 8.48 (s, 1 H), 7.37-7.33 (m, 2 H), 7.25-7.19 (m, 2 H), 7.03-6.99 (m, 3 H), 6.94 (s, 1
16
17 H), 6.87 (d, J = 8.4 Hz, 1 H), 6.67 (t, J = 7.4 Hz, 1 H), 6.32 (d, J = 7.2 Hz, 1 H), 2.43
18
19
20 (s, 3 H), 2.23 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ = 170.3, 149.1, 140.1, 139.9,
21
22 138.5, 136.4, 134.4, 129.9, 129.6, 129.5, 127.5, 127.3, 126.4, 125.5, 122.3, 120.3,
23
24
25 119.4, 21.3, 19.9; ESI-HRMS Calcd for C22H22NO2 [M + H]+ 332.1645, found
26
27 332.1653.
28
29
30
N-(2-Hydroxyphenyl)-2-phenyl-5-methyl benzamide (5h). Yield: 85%, 77 mg; white
31
32
33 solid; mp 165-167 oC; Rf = 0.25; 1H NMR (400 MHz, CDCl3): δ = 9.04 (s, 1 H), 7.71
34
35
36
(s, 1 H), 7.47-7.37 (m, 6 H), 7.32 (d, J = 7.6 Hz, 1 H), 7.16 (s, 1 H), 7.04 (t, J = 7.6
37
38 Hz, 1 H), 6.95 (d, J = 8.0 Hz, 1 H), 6.66 (t, J = 7.6 Hz, 1 H), 5.88 (d, J = 7.6 Hz, 1 H),
39
40 13
41
2.44 (s, 3 H); C NMR (100 MHz, CDCl3): δ = 169.3, 149.1, 139.6, 138.2, 137.4,
42
43 133.0, 132.3, 130.5, 130.5, 129.3, 129.0, 128.2, 127.4, 125.4, 122.1, 120.2, 119.9,
44
45
46 21.0; ESI-HRMS Calcd for C20H17NNaO2 [M + Na]+ 326.1151, found 326.1151.
47
48
49 N-(2-Hydroxyphenyl)-2-(tolyl)-5-methyl benzamide (5i). Yield: 94%, 89.5 mg; white
50
51 solid; mp 185-187 oC; Rf = 0.53; 1H NMR (400 MHz, CDCl3): δ = 9.07 (s, 1 H), 7.65
52
53
54 (s, 1 H), 7.34-7.23 (m, 7 H), 7.03 (t, J = 7.6 Hz, 1 H), 6.92 (d, J = 8.4 Hz, 1 H), 6.66
55
56 13
(t, J = 7.6 Hz, 1 H), 6.01 (d, J = 8.0 Hz, 1 H), 2.40 (s, 6 H); C NMR (100 MHz,
57
58
59
60
ACS Paragon Plus Environment
Page 25 of 30 The Journal of Organic Chemistry

1
2
3
4 CDCl3): δ = 169.5, 149.0, 138.0, 137.8, 137.5, 136.7, 133.0, 132.2, 130.6, 130.3,
5
6 129.9, 128.9, 127.2, 125.6, 122.1, 120.1, 119.7, 21.2, 21.0; ESI-HRMS Calcd for
7
8
9 C21H19NNaO2 [M + Na]+ 340.1308, found 340.1307.
10
11
12 N-(2-Hydroxyphenyl)-2-(p-methoxylphenyl)-5-methyl benzamide (5j). Yield: 93%,
13
14
15 93 mg; white solid; mp 160-162 oC; Rf = 0.23; 1H NMR (400 MHz, CDCl3): δ = 9.04
16
17 (s, 1 H), 7.63 (s, 1 H), 7.38 (s, 1 H), 7.34-7.24 (m, 4 H), 7.03 (t, J = 7.6 Hz, 1 H),
18
19
20 6.96-6.91 (m, 3 H), 6.68 (t, J = 7.6 Hz, 1 H), 6.15 (d, J = 8.0 Hz, 1 H), 3.81 (s, 3 H),
21
22 13
2.40 (s, 3 H); C NMR (100 MHz, CDCl3): δ = 169.6, 159.6, 148.9, 137.6, 137.0,
23
24
25 133.0, 132.2, 131.7, 130.6, 130.3, 130.2, 127.2, 125.6, 122.2, 120.2, 119.6, 114.6,
26
27 55.5, 21.0; ESI-HRMS Calcd for C21H20NO3 [M + H]+ 334.1438, found 334.1419.
28
29
30
N-(2-Hydroxyphenyl)-2-(p-bromophenyl)-5-methyl benzamide (5k). Yield: 90%,
31
32
o 1
33 103 mg; white solid; mp 191-193 C; Rf = 0.40; H NMR (400 MHz, DMSO-d6): δ =
34
35
36
9.60 (s, 1 H), 9.38 (s, 1 H), 7.58-7.52 (m, 3 H), 7.47 (s, 1 H), 7.40-7.33 (m, 4 H), 6.98
37
38 (t, J = 7.2 Hz, 1 H), 6.84 (d, J = 7.6 Hz, 1 H), 6.77 (t, J = 7.2 Hz, 1 H), 2.41 (s, 3 H);
39
40 13
41
C NMR (100 MHz, DMSO-d6): δ = 167.8, 148.7, 139.2, 137.1, 136.1, 135.3, 131.1,
42
43 130.6, 130.5, 129.8, 128.6, 125.8, 125.4, 123.0, 120.6, 118.9, 115.9, 20.5; ESI-HRMS
44
45
46 Calcd for C20H17BrNO2 [M + H]+ 382.0437, found 382.0452.
47
48
49 N-(2-Hydroxyphenyl)-2-(p-nitrophenyl)-5-methyl benzamide (5l). Yield: 87%, 91
50
51 mg; white solid; mp 184-186 oC; Rf = 0.11; 1H NMR (400 MHz, DMSO-d6): δ = 9.59
52
53
54 (s, 1 H), 9.47 (s, 1 H), 8.25 (d, J = 8.0 Hz, 2 H), 7.71 (d, J = 8.0 Hz, 2 H), 7.54 (s, 2
55
56
H), 7.43 (s, 2 H), 6.98 (t, J = 7.2 Hz, 1 H), 6.84 (d, J = 7.6 Hz, 1 H), 6.77 (t, J = 7.4
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 26 of 30

1
2
3 13
4 Hz, 1 H), 2.44 (s, 3 H); C NMR (100 MHz, DMSO-d6): δ = 167.4, 149.0, 147.0,
5
6 146.5, 138.2, 136.4, 134.7, 130.7, 130.0, 129.7, 128.8, 125.6, 125.6, 123.5, 123.4,
7
8
9 118.9, 115.8, 20.6; ESI-HRMS Calcd for C20H17N2O4 [M + H]+ 349.1183, found
10
11 349.1186.
12
13
14
15 N-(2-Hydroxyphenyl)-2-(m-methylphenyl)-5-methyl benzamide (5m). Yield: 92%,
16
17 88 mg; white solid; mp 170-172 oC; Rf = 0.38; 1H NMR (400 MHz, CDCl3): δ = 9.06
18
19
20 (s, 1 H), 7.72 (s, 1 H), 7.37-7.30 (m, 3 H), 7.27-7.21 (m, 4 H), 7.04 (t, J = 7.6 Hz, 1
21
22 H), 6.95 (d, J = 7.6 Hz, 1 H), 6.67 (t, J = 7.4 Hz, 1 H), 5.88 (d, J = 8.0 Hz, 1 H), 2.43
23
24
25 (s, 3 H), 2.36 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 169.4, 149.2, 139.6, 139.1,
26
27 138.0, 137.6, 132.8, 132.2, 130.6, 130.5, 129.7, 129.2, 129.0, 127.4, 126.1, 125.5,
28
29
30 122.1, 120.2, 119.9, 21.4, 21.0; ESI-HRMS Calcd for C21H19KNO2 [M + K]+
31
32 356.1047, found 356.1031.
33
34
35
36
Supporting Information
37
38 The Supporting Information is available free of charge on the ACS Publications
39
40
41
website at DOI: . 1H/13C NMR spectra for all products, the 1H NMR of the products
42
43 from KIE experiment, and the crystal structure of 4b (PDF), crystallographic data of
44
45
46 4b (CIF)
47
48 AUTHOR INFORMATION
49
50
51 Corresponding Authors
52
53 *E-mail: wanjieping@[Link] (J.-P.W.).
54
55
56 *E-mail: chemliuyunyun@[Link] (Y.L.).
57
58 Notes
59
60
ACS Paragon Plus Environment
Page 27 of 30 The Journal of Organic Chemistry

1
2
3
4 The authors declare no competing financial interest.
5
6
7
8 ACKNOWLEDGEMENTS
9
10
11 The work is financially supported by National Natural Science Foundation of
12
13 China (21562024, 21562025) and the Science Fund for Distinguished Young Scholars
14
15
16 of Jiangxi Province (20162BCB23023).
17
18
19 REFERENCES
20
21
22 1 For selected reviews, see: (a) Mcmurray, L.; O’Hara, F.; Gaunt, M. J. Chem. Soc.
23
24
25 Rev. 2011, 40, 1885. (b) Yamaguchi, J.; Yamaguchi, A. D.; Itami, K. Angew. Chem.
26
27 Int. Ed. 2012, 51, 8960. (c) Chen, D. Y.-K.; Youn, S. W. Chem. Eur. J. 2012, 18,
28
29
30 9452. (d) Tao, P.; Jia, Y. Sci. China Chem. 2016, 59, 1109.
31
32
33 2 (a) Dai, H.-X.; Stepan, A. F.; Plummer, M. S.; Zhang, Y.-H.; Yu, J.-Q. J. Am.
34
35
Chem. Soc. 2011, 133, 7222. (b) Schönherr, H.; Cernak, T.; Angew. Chem. Int. Ed.
36
37
38 2013, 52, 12256. (c) Shan, G.; Yang, Y.; Ma, L.; Rao, Y. Angew. Chem. Int. Ed.
39
40
2012, 51, 13070. (d) He, J.; Hamnn, L. G.; Davies, H. M. L.; Beckwith, R. E. J.
41
42
43 Nat. Commun., 2015, 6, 5943. (e) Tang, S.; Liu, K.; Liu, C.; Lei, A. Chem. Soc.
44
45
Rev. 2015, 44, 1070.
46
47
48
3 For reviews, see: (a) Okamoto, K.; Zhang, J.; Housekeeper, J. B.; Marder, S. R.;
49
50
51 Luscombe, C. K. Macromolecules 2013, 46, 8059. (b) Kuninobu, Y.; Sueki, S.;
52
53
Synthesis 2015, 47, 3823. (c) Thierry, B.; Corinne, F. Synthesis 2016, 48, 3879.
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 28 of 30

1
2
3
4 4 For selected reviews, see: (a) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110,
5
6 1147. (b) Colby, D. A.; Bergman, T. G.; Ellman, J. A. Chem. Rev. 2010, 110, 624.
7
8
9 (c) Zhang, F.; Spring, D. R. Chem. Soc. Rev. 2014, 43, 6906. (d) Chen, Z.; Wang,
10
11 B.; Zhang, J.; Yu, W.; Liu, Z.; Zhang, Y. Org. Chem. Front. 2015, 2, 1107. (e) Ros,
12
13
14 A.; Fernández, R.; Lassaletta, J. M. Chem. Soc. Rev. 2014, 43, 3229. (f) Daugulis,
15
16 O.; Roane, J.; Tran, L. D. Acc. Chem. Res. 2015, 48, 1053. (g) Sun, H.; Guimond,
17
18
19 N.; Huang, Y. Org. Biomol. Chem. 2016, 14, 8389.
20
21
22 5 For reviews, see: (a) Zhang, M.; Zhang, Y.; Jie, X.; Zhao, H.; Li, G.; Su, W. Org.
23
24 Chem. Front. 2014, 1, 843. (b) Drapeau, M. P.; Gooßen, L. J. Chem. Eur. J. 2016,
25
26
27 22, 18654.
28
29
30 6 (a) Corbet, M.; De Campo, F. Angew. Chem. Int. Ed. 2013, 52, 9896. (b) Wan,
31
32 J.-P.; Liu, Y. Org. Chem. Front., 2016, 3, 768. (c) Liu, J.; Chen, G.; Tan, Z. Adv.
33
34
35 Synth. Catal. 2016, 358, 1174. (d) Shabashov, D.; Daugulis, O. J. Am. Chem. Soc.
36
37 2010, 132, 3965.
38
39
40 7 For selected examples, see: (a) Wang, X.-C.; Gong, W.; Fang, L.-Z.; Zhu, R.-Y.;
41
42
43 Li, S.; Engle, K. M.; Yu, J.-Q. Nature 2015, 519, 334. (b) Sun, F.; Li, M.; He, C.;
44
45 Wang, B.; Li, B.; Sui, X.; Gu, Z. J. Am. Chem. Soc. 2016, 138, 7456. (c) Du, C.; Li,
46
47
48 P.-X.; Zhu, X.; Suo, J.-F.; Niu, J.-L.; Song, M.-P. Angew. Chem. Int. Ed. 2016, 55,
49
50
13571. (d) Wei, J.; Jiang, J.; Xiao, X.; Lin, D.; Dong, Y.; Ke, Z.; Jiang, H.; Zeng,
51
52
53 W. J. Org. Chem. 2016, 81, 946. (e) Shen, C.; Xu, J.; Ying, B.; Zhang, P.;
54
55
ChemCatChem 2016, 8, 3560. (f) Ricci, P.; Krämer, K.; Cambeiro, X. C.; Larrosa,
56
57
58 I. J. Am. Chem. Soc. 2013, 135, 13258.
59
60
ACS Paragon Plus Environment
Page 29 of 30 The Journal of Organic Chemistry

1
2
3
4 8 (a) Xie, F.; Yu, S.; Qi, Z.; Li, X. Angew. Chem. Int. Ed. 2016, 55, 15351. (b) Hua,
5
6 Y.; Asgari, P.; Avullala, T.; Jeon, J. J. Am. Chem. Soc. 2016, 138, 7892. (c) Zhang,
7
8
9 Y.; Zhao, H.; Zhang, M.; Su, W. Angew. Chem. Int. Ed. 2015, 54, 3817. (d) Wu, Y.;
10
11 Feng, L.-J.; Lu, X.; Kwong, F. Y.; Luo, H.-B. Chem. Commun. 2014, 50, 15352. (e)
12
13
14 Huang, X.; Huang, J.; Du, C.; Zhang, X.; Song, F.; You, J. Angew. Chem. Int. Ed.
15
16 2013, 52, 12970. (f) Chiong, H. A.; Pham, Q.-N.; Daugulis, O. J. Am. Chem. Soc.
17
18
19 2007, 129, 9879.
20
21
22 9 (a) Huang, L.; Biafora, A.; Zhang, G.; Bragoni, V.; Gooßen, L. J. Angew. Chem.
23
24 Int. Ed. 2016, 55, 6993. (b) Biafora, A.; Khan, B. A.; Bahri, J.; Hewer, J. M.;
25
26
27 Gooßen, L. J. Org. Lett. 2017, 19, 1232.
28
29
30 10 (a) Zhang, F.-L.; Hong, K.; Park, H.; Yu, J.-Q. Science 2016, 351, 252. (b) Liu,
31
32 Y.; Ge, H. Nat. Chem. 2017, 9, 26. (c) Xu, J.; Liu, Y.; Wang, Y.; Li, Y.; Xu, X.;
33
34
35 Jin, Z. Org. Lett. 2017, 19, 1562. (d) Zhang, Y.-F.; Wu, B.; Shi, Z.-J. Chem. Eur. J.
36
37 2016, 22, 17808.
38
39
40 11 (a) Chen, S.; Yu, J.; Jiang, Y.; Chen, F.; Cheng, J. Org. Lett. 2013, 15, 4754. (b)
41
42
43 Muralirajan, K.; Cheng, C.-H. Adv. Synth. Catal. 2014, 356, 1571. (c) Kumar, R.;
44
45 Arigela, R. K.; Kundu, B. Chem. Eur. J. 2015, 21, 11807. (d) Zi, W.; Wang, Y.-M.;
46
47
48 Toste, F. D. J. Am. Chem. Soc. 2014, 136, 12864. (e) Arigela, R. K.; Kumar, R.;
49
50
Joshi, T.; Mahar, R.; Kundu, B. RSC Adv. 2014, 4, 57749. (f) Teskey, C. J.; Sohel,
51
52
53 S. M. A.; Bunting, D. L.; Modha, S. G.; Greaney, M. F. Angew. Chem. Int. Ed.
54
55
2017, 56, 5263. (g) Xu, Y.; Young, M. C.; Wang, C.; Magness, D. M.; Dong, G.
56
57
58 Angew. Chem. Int. Ed. 2016, 55, 9084.
59
60
ACS Paragon Plus Environment
 The Journal of Organic Chemistry Page 30 of 30

1
2
3
4 12 Liu, Y.; Zhang, Y.; Huang, M.; Wan, J.-P. RSC Adv. 2015, 5, 46192.
5
6
7 13 Liu, Y.; Huang, B.; Cao, X.; Wan, J.-P. ChemCatChem 2016, 8, 1470.
8
9
10 14 Liu, Y.; Zhang, Y.; Cao, X.; Wan, J.-P. Beilstein J. Org. Chem. 2016, 12, 1122.
11
12
13 15 Liu, Y.; Huang, M.; Wei, L. Asian J. Org. Chem. 2017, 6, 41.
14
15
16 16 During the preparation of this manuscript, Watkins et al reported that the
17
18 N-(2-aminophenyl)acetamide which could be generated from the N-acylatio of
19
20
21 simple commercial o-phenylenediamine is applicable DG in the mono-Ar-H
22
23 arylation of benzamides, but the prior installation of the DG via separate step is
24
25
26 also employed: Reddy, M. D.; Blanton, A. N.; Watkins, E. B. J. Org. Chem.
27
28 2017, 82, 5080.
29
30
31 17 CCDC 1546993 (4b) contains the supplementary crystallographic data for this
32
33
34 [Link] data can be obtained free of charge from the Cambridge
35
36 Crystallographic Data Centre via [Link]. [Link]/data_request/cif.
37
38
39 18 Zaitsev, V. G.; Shabashove, D.; Daugulis, O. J. Am. Chem. Soc. 2005, 127,
40
41
42 13154.
43
44
45 19 Tsang, W. C. P.; Zhang, N.; Buchwald, S. L, J. Am. Chem. Soc. 2005, 127,
46
47
48 14560.
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment