Nickel-Catalyzed ortho-C-H Thiolation of N-Benzoyl α-Amino Acid Derivatives

Article abstract of DOI:10.1021/acs.joc.6b01702

We developed the first nickel-catalyzed direct ortho-thiolation of N-benzoyl α-amino acid derivatives. This novel strategy showed wide generality, functional tolerance, and high regioselectivity. In addition, dipeptide derivatives were also compatible with this transformation system, providing a potential protocol for the direct modification of peptide derivatives.

Full text of DOI:10.1021/acs.joc.6b01702

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Article
Nickel-Catalyzed ortho-C-H Thiolation of N-
Benzoyl alpha-Amino Acid Derivatives
Feng Gao, Wei Zhu, Dengyou Zhang, Shuangjie Li, Jiang Wang, and Hong Liu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01702 • Publication Date (Web): 14 Sep 2016
Downloaded from http://pubs.acs.org on September 15, 2016
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Nickel-Catalyzed ortho-C-H Thiolation of N-
Benzoyl α-Amino Acid Derivatives
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Feng Gao, Wei Zhu, Dengyou Zhang, Shuangjie Li, Jiang Wang, and Hong Liu*
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CAS Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy
of Sciences, 555 Zuchongzhi Road, Shanghai 201203, China
hliu@simm.ac.cn (Hong Liu)
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Graphic Abstract
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Abstract
We developed the first nickel-catalyzed direct ortho-thiolation of N-benzoyl α-amino acid
derivatives. This novel strategy showed wide generality, functional tolerance and high regioselectivity.
In addition, dipeptide derivatives were also compatible with this transformation system, providing a
potential protocol for the direct modification of peptide derivatives.
Introduction
Functionalized amino acid derivatives have been employed widely as useful substrates in medicinal
chemistry and the pharmaceutical industry for their broad biological activities1 and facile membrane
permeability.2 Among them, ortho-thio substituted N-benzoyl α-amino acid derivatives are found
frequently as building blocks in bioactive compounds (Figure 1).3 Traditionally, the construction of
such scaffolds is achieved by the cross coupling reactions between aryl-halides and thiol/disulfides,
suffering from harsh reaction conditions, low substrate scopes and pre-functionalization of the
substrates.4 Thus, there remains the need to develop efficient and environmentally friendly synthetic
methods to elaborate amino acid derivatives.
Figure 1. Bioactive ortho-thio substituted N-benzoyl α-amino acid derivatives.
In recent decades, transition-metal-catalyzed direct C-H functionalization has made great progress,
in which diverse transformations and good regioselectivity have been realized with the assistance of
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various directing groups.5 Very recently, environmentally friendly and inexpensive amino acid
moieties have been employed as novel directing groups in C-H activation for the direct modification
of amino acid derivatives. Chatani reported an elegant work of ortho-C(sp2)–H arylation/alkylation
using α-amino ester moieties as bidentate directing groups (Scheme 1A).6 By the employment of
similar strategy, direct C(sp3)–H functionalization of the amino acid derivatives has been
accomplished by Yu’s,7 and Hong’s group.8 Mostly, these protocols demonstrated the formation of C-
C bonds via C-H cleavage using palladium as the catalyst. Recently, nickel catalysts in C-H activation
reactions have attracted increasing attention owing to their abundance, low cost and relatively less
toxicity.9,10 Given the importance of ortho-thio substituted N-benzoyl α-amino acid derivatives, we
proposed the construction of such privilege frameworks via nickel-catalyzed direct C-H activation.
Herein, we report the first example of nickel-catalyzed C-H thiolation of N-benzoyl α-amino acid as
well as dipeptide derivatives (Scheme 1B).
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Scheme 1. Nickel-Catalyzed C(sp2)–H Thiolation.
Results and Discussion
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To verify the hypothesis, we initiated our studies by investigating the reaction with a series of N-
benzoyl α-amino acid derivatives. The treatment of 1a with disulfide 2a in the presence of nickel
catalyst and base afforded the desired thiolated product 3a in 76% yield (Table 1, entries 1-5), while
other substrates were not effective. This result suggested that bis-NH of amides were essential for the
nickel-catalyzed C-H activation. The optimization of nickel salts revealed that Ni(OTf)2 was the most
effective catalyst to provide product 3a, giving a yield of 93% (entries 6-10). Further screening of
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t
bases determined that BuOLi was the best (entries 11-13). The efficiency of the reaction was also
significantly affected by different solvents (entries 14-18), with DMF being identified as the optimal
solvent. No desired product was obtained in non-polar or protonic solvents, while the use of DMSO
resulted in a dramatic decrease yield.
Table 1. Optimization of Reaction Conditionsa
Entry
DG
1aa
1ab
1ac
1ad
1a
[Ni]
NiCl2
Base
Solvent
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Yield (%)
trace
trace
trace
trace
76
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tBuOLi
tBuOLi
tBuOLi
tBuOLi
tBuOLi
tBuOLi
tBuOLi
tBuOLi
tBuOLi
NiCl2
NiCl2
NiCl2
NiCl2
NiBr2
80
1a
NiI2
88
1a
Ni(acac)2
Ni(OAc)2
81
1a
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tBuOLi
tBuONa
tBuOK
Na2CO3
tBuOLi
tBuOLi
tBuOLi
tBuOLi
tBuOLi
DMF
93
88
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Ni(OTf)2
1a
1a
1a
1a
1a
1a
1a
1a
1a
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
DMF
DMF
84
9
DMF
trace
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DMSO
Toluene
DCE
trace
trace
trace
trace
Dioxane
tAmylOH
a Reaction conditions: 1 (0.2 mmol), 2a (0.4 mmol), [Ni] (10 mol%), base (2 equiv), solvent
(1 mL) in air at 120 °C.
With the optimized reaction conditions in hand, we investigated the scope of N-benzoyl α-amino
acid derivatives. Generally, this thiolation reaction tolerated various substituents both on the aromatic
ring and α-amino acid moieties, and generated the desired products in moderate to high yields (Table
2). Benzamides bearing a large group in the ortho-position, such as trifluoromethyl and phenyl groups,
gave moderate yields, probably due to the steric hindrance while halogen could be tolerated well under
standard conditions (3b-3d). When meta-substituted benzamides were employed, the C-H bond
thiolation took place at the less sterically hindered position irrespective of the electronic nature of the
substituents (3e-3g). The unsubstituted and para-substituted benzamides afforded a mixture of mono-
and di-thiolated products, while exclusive di-thiolated products were obtained in good yields by
increasing the amounts of disulfide, nickel catalyst and base (3h-3j). Multisubstituted benzamide
derivative and naphthamide provided the desired products in high yields (3k and 3l). Furthermore,
heterocycles were also compatible with the optimal conditions (3m and 3n). Next, the reaction
efficiency of different α-amino acid moieties were evaluated. Cyclic amino acid derivatives proceeded
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smoothly and produced the corresponding products in high yields (3o and 3p). Substrates bearing
natural α-amino acid moieties, such as alanine, valine, leucine and phenylalanine, worked well under
the standard conditions (3q-3t). Notably, the chirality at the α-position of valine was not influenced
after the transformation (97% ee). In addition, dipeptide derivatives (1u and 1v) were also effective
substrates, indicating that the reaction system could be a potential strategy for direct modification of
peptides. Importantly, the C(sp2)-H thiolation was carried out on a gram scale without any additives
to afford 3a in 90% yield (Scheme 2).
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Table 2. Scope of N-Benzoyl α-Amino Acid Derivativesa
3a, 93%
3d, 58%b
3g, 75%
3b, 64%c
3c, 41%
3f, 74%
3e, 71%
3h, 80%
3h’, 76%c
(mono:di = 1:1.4)
3i, 76%c
3j, 77%c
3k, 85%
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3l, 87%
3m, 35%b
3n, 79%
3q, 73%
3t, 54%
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3o, 90%
3p, 80%
3r, 81% (97% ee) d
3s, 76%
3u, 67%e
3v, 30%e
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a Reaction conditions: 1 (0.2 mmol), 2a (0.4 mmol), Ni(OTf)2 (10 mol%), tBuOLi (0.4 mmol), DMF
b
c
t
d
(1 mL) in air at 120 °C. 15 h. 2a (0.6 mmol), Ni(OTf)2 (15 mol%) and BuOLi (0.6 mmol).
100 °C. e Ni(OTf)2 (20 mol%) and tBuOLi (0.6 mmol).
Scheme 2. Gram-scale C(sp2)–H Thiolation.
Next, the scope of disulfides was further tested (Table 3). In general, various disulfides and diselanes
proceeded smoothly to provide the corresponding products. The introduction of electron-donating
group at the para- or meta-position of diphenyl disulfides had no influence on the yield (4b, 4c and
4f), while meta-nitro substituted diphenyl disulfides gave a relative lower yield (4h). Contrastingly,
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halogen-substituted diphenyl disulfides produced the corresponding products in excellent yields,
guaranteeing further transformation (4d and 4g). Ortho-substituted disulfide could also furnish the
product with a slightly decreasing yield, probably because of interference with the oxidative addition
process (4i). Importantly, heteroaromatic disulfide and diphenyl diselanes were also compatible with
the reaction conditions, delivering the products in moderate to good yields (4j-4m). Unfortunately, no
desired thiolated product was observed, when dibenzyldisulfane and dipropyldisulfane were applied
(4n and 4o).
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Table 3. Scope of Disulfidesa
4b, 85%
4f, 83%
4j, 72%b
4c, 81%
4g, 94%
4k, 58%b
4d, 98%
4h, 43%
4l, 54%b
4e, 85%b
4i, 71%
4m, 42%b
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4n, 0%
4o, 0%
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a Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), Ni(OTf)2 (10 mol%), tBuOLi (2 equiv),
DMF (1 mL) in air at 120 °C. b 18 h.
To understand the reaction mechanism, we first performed a radical scavenger experiment (Scheme
3A). The result revealed that the reaction efficiency was not affected by TEMPO (1 equiv.), indicating
that it likely did not involve a single electron transfer (SET) process. Furthermore, an intermolecular
competition experiment between 1f and 1g was carried out and the substrate bearing an electron-
withdrawing substituent reacted with higher relative rate (Scheme 3B), which suggested that C-H bond
cleavage might be influenced by its acidity. A detailed mechanism remains to be elucidated.
Scheme 3. Mechanistic Investigations
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Conclusion
In conclusion, we developed the first nickel-catalyzed direct ortho-thiolation of N-benzoyl α-amino
acid derivatives. This method is widely applicable and shows high functional tolerance and high
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regioselectivity. Dipeptide derivatives were also compatible, representing a potential protocol for the
direct modification of peptide derivatives. It also provides a straightforward approach for the
construction of ortho-thio substituted N-benzoyl α-amino acid derivatives, which are identified as
privilege scaffolds with wide potential bioactivities in pharmaceuticals. Therefore, this modified
strategy will be of importance to medicinal chemists.
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Experimental Section
General Information. Unless otherwise noted, the reagents (chemicals) were purchased from
commercial sources, and used without further purification. Water was deionized before used.
Analytical thin layer chromatography (TLC) was HSGF 254 (0.15-0.2 mm thickness). Compound
spots were visualized by UV light (254 nm). Column chromatography was performed on silica gel
FCP 200-300. NMR spectra were run on 400 or 500 MHz instrument. Chemical shifts were reported
in parts per million (ppm, δ) downfield from tetramethylsilane. Proton coupling patterns are described
as singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), and broad (br). Low- and high-resolution
mass spectra (LRMS and HRMS) were measured on spectrometer.
General Procedure for the Preparation of Substrates 1a-v. To a mixture of 2-((tert-
butoxycarbonyl)amino)-2-methylpropanoic acid (25.00 g, 123.01 mmol) and HOBt (18.28 g, 135.31
mmol) in 200 mL of DCM was added TEA (56.27 mL, 405.93 mmol), followed by addition of EDCI
(25.94 g, 135.31 mmol). The resulting mixture was stirred for 10 min and then methanamine
hydrochloride (8.31 g, 123.01 mmol) was added. The reaction was stirred overnight. The mixture was
diluted with DCM and the organic layer was washed with saturated sodium carbonate, brine, dried
over anhydrous Na2SO4 and concentrated under vacuum to give a white solid (23.10 g, 87%).
To a mixture of tert-butyl (2-methyl-1-(methylamino)-1-oxopropan-2-yl)carbamate (23.10 g, 106.81
mmol) in 150 mL of dioxane was added dropwise a solution of HCl in dioxane (4 N, 150 mL) at 0 °C.
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The reaction was stirred at room temperature for 3 h. Then the mixture was concentrated under vacuum
to give the crude product as a white solid (15.80 g, 97%).
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To an ice-cooled solution of 2-amino-N,2-dimethylpropanamide hydrochloride (1.50 g, 9.83 mmol) in
40 mL of DCM was added TEA (4.09 mL, 29.48 mmol), followed by addition of corresponding
benzoyl chloride (1.08 mmol) dropwise. The resulting mixture was stirred at room temperature for 6
h. Then the reaction was quenched by water and extracted with DCM. The combined organic layer
was washed with brine, dried over anhydrous Na2SO4 and concentrated under vacuum. The residue
was purified by silica gel column to afford the title compound as a white solid.
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General Procedure for Nickel-Catalyzed ortho-C-H Thiolation of N-Benzoyl α-Amino
Derivatives. A Schlenk tube equipped with a magnetic stir bar was charged with Ni(OTf)2 (7.1 mg,
10 mol%), tBuOLi (32.1 mg, 0.40 mmol), substrate 1 (0.20 mmol) and disulfide 2 (0.4 mmol) and then
capped with septa. 1 mL of DMF was charged to the vial via syringe, and then the resulting mixture
was stirred in a pre-heated oil bath at 120 °C for 12 h. After the reaction was completed, the solvent
was removed under vacuum and the residue was purified by silica gel column (PE/EA = 2:3) to afford
desired thiolated product.
Analytical Characterization Data of Products.
2-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(phenylthio)benzamide
(3a):
Compound 3a was prepared as described in general procedure for nickel catalyzed ortho-C-H
1
thiolation of N-benzoyl α-amino derivatives. White solid, 64 mg, 93% yield. Mp: 144-146 °C. H
NMR (400 MHz, DMSO-d6) δ 8.47 (s, 1H), 7.37 – 7.20 (m, 8H), 7.13 (dd, J = 7.5, 0.8 Hz, 1H), 2.56
(d, J = 4.7 Hz, 3H), 2.30 (s, 3H), 1.41 (s, 6H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 174.3, 167.1,
141.2, 135.9, 135.7, 130.8, 130.6, 130.1, 129.9, 129.41, 129.37, 127.1, 56.6, 26.1, 25.0, 18.8. LRMS
(ESI) [M+H]+ found: 343.0. HRMS (ESI) [M+Na]+ calcd for C19H22O2N2NaS: 365.1294, found:
365.1288. Anal. Calcd for C19H22O2N2S: C, 66.64; H, 6.48; N, 8.18; found: C, 66.46; H, 6.51; N, 8.18.
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N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-3-(phenylthio)-[1,1'-biphenyl]-2-carboxamide
(3b): Compound 3b was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 52 mg, 64% yield. Mp: 174-176 °C . H
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NMR (500 MHz, DMSO-d6) δ 8.36 (s, 1H), 7.49 – 7.37 (m, 10H), 7.36 – 7.29 (m, 2H), 7.27 (d, J =
7.8 Hz, 1H), 6.65 (q, J = 4.7 Hz, 1H), 2.44 (d, J = 4.7 Hz, 3H), 1.17 (s, 6H). 13C {1H} NMR (125 MHz,
DMSO-d6) δ 174.0, 166.5, 140.0, 139.42, 139.39, 134.9, 132.3, 131.3, 131.1, 129.51, 129.49, 129.1,
128.8, 128.0, 127.6, 56.7, 25.9, 24.6. LRMS (ESI) [M+H]+ found: 405.0. HRMS (ESI) [M+Na]+
calcd for C24H24O2N2NaS: 427.1451, found: 427.1445.
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N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2-(phenylthio)-6-(trifluoromethyl)benzamide
(3c): Compound 3c was prepared as described in general procedure for nickel catalyzed ortho-C-H
1
thiolation of N-benzoyl α-amino derivatives. White solid, 32 mg, 41% yield. Mp: 166-168 °C. H
NMR (500 MHz, DMSO-d6) δ 8.68 (s, 1H), 7.74 (d, J = 7.5 Hz, 1H), 7.62 – 7.51 (m, 2H), 7.49 – 7.38
(m, 4H), 7.38 – 7.33 (m, 1H), 7.27 (d, J = 4.2 Hz, 1H), 2.58 (d, J = 4.5 Hz, 3H), 1.45 (s, 6H). 13C {1H}
NMR (125 MHz, MeOD) δ 176.9, 167.7, 138.1, 137.5, 137.2, 135.2, 133.2, 131.3, 130.8, 128.6, 129.0
(q, J = 31.8 Hz), 126.5 (q, J = 4.7 Hz), 125.0 (q, J = 273.7 Hz), 59.1, 26.6. LRMS (ESI) [M+H]+
found: 397.0. HRMS (ESI) [M+Na]+ calcd for C19H19O2N2F3NaS: 419.1012, found: 419.1006.
2-Fluoro-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(phenylthio)benzamide
(3d):
Compound 3d was prepared as described in general procedure for nickel catalyzed ortho-C-H
1
thiolation of N-benzoyl α-amino derivatives. White solid, 40 mg, 58% yield. Mp: 163-166 °C. H
NMR (500 MHz, DMSO-d6) δ 8.68 (s, 1H), 7.44 – 7.33 (m, 6H), 7.25 – 7.16 (m, 2H), 6.99 (d, J = 7.8
Hz, 1H), 2.59 (d, J = 4.6 Hz, 3H), 1.43 (s, 6H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 173.8, 162.3,
158.5 (d, J = 247.7 Hz), 135.1 (d, J = 4.0 Hz), 133.9, 131.7, 131.0 (d, J = 8.8 Hz), 129.6, 128.0, 127.8
(d, J = 20.5 Hz), 127.4, 114.5 (d, J = 11.0 Hz), 56.8, 26.1, 25.0. LRMS (ESI) [M+H]+ found: 347.0.
HRMS (ESI) [M+Na]+ calcd for C18H19O2N2FNaS: 369.1043, found: 369.1042.
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5-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2-(phenylthio)benzamide
(3e):
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Compound 3e was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 49 mg, 71%. Mp: 149-152 °C. H NMR
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(500 MHz, DMSO-d6) δ 8.33 (s, 1H), 7.46 (d, J = 1.2 Hz, 1H), 7.42 (q, J = 4.6 Hz, 1H), 7.37 – 7.32
(m, 2H), 7.32 – 7.24 (m, 3H), 7.19 (dd, J = 8.0, 1.3 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 2.56 (d, J = 4.6
Hz, 3H), 2.33 (s, 3H), 1.39 (s, 6H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 174.2, 167.0, 139.1, 136.8,
135.7, 132.1, 130.85, 130.79, 129.5, 129.4, 128.8, 127.2, 56.4, 26.1, 25.1, 20.4. LRMS (ESI) [M+H]+
found: 343.0. HRMS (ESI) [M+Na]+ calcd for C19H22O2N2NaS: 365.1294, found: 365.1292.
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5-Methoxy-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2-(phenylthio)benzamide
(3f):
Compound 3f was prepared as described in general procedure for nickel catalyzed ortho-C-H
1
thiolation of N-benzoyl α-amino derivatives. White solid, 53 mg, 74% yield. Mp: 162-165 °C. H
NMR (500 MHz, DMSO-d6) δ 8.35 (s, 1H), 7.40 (q, J = 4.5 Hz, 1H), 7.33 – 7.26 (m, 3H), 7.23 – 7.17
(m, 4H), 7.02 (dd, J = 8.7, 2.9 Hz, 1H), 3.82 (s, 3H), 2.55 (d, J = 4.6 Hz, 3H), 1.35 (s, 6H). 13C {1H}
NMR (125 MHz, DMSO-d6) δ 174.1, 166.7, 159.1, 142.4, 137.2, 135.9, 129.2, 128.9, 126.3, 121.4,
116.0, 113.9, 56.5, 55.6, 26.1, 25.0. LRMS (ESI) [M+H]+ found: 359.0. HRMS (ESI) [M+H]+ calcd
for C19H23O3N2S: 359.1424, found: 359.1422.
N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2-(phenylthio)-5-(trifluoromethyl)benzamide
(3g): Compound 3g was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 59 mg, 75% yield. Mp: 162-163 °C. H
NMR (500 MHz, DMSO-d6) δ 8.67 (s, 1H), 8.06 (d, J = 1.4 Hz, 1H), 7.68 – 7.62 (m, 2H), 7.56 – 7.44
(m, 5H), 6.99 (d, J = 8.4 Hz, 1H), 2.60 (d, J = 4.6 Hz, 3H), 1.44 (s, 6H). 13C {1H} NMR (125 MHz,
DMSO-d6) δ 173.9, 165.6, 142.7, 135.6, 134.2, 131.9, 130.1, 129.3, 128.4, 126.6 (q, J = 3.5 Hz), 125.5
(q, J = 32.3 Hz), 125.2 (q, J = 3.5 Hz), 125.1 (q, J = 272.5 Hz), 56.6, 26.2, 25.2. LRMS (ESI) [M+H]+
found: 396.9. HRMS (ESI) [M+Na]+ calcd for C19H19O2N2F3NaS: 419.1012, found: 419.1007.
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N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2-(phenylthio)benzamide (3h): Compound 3h
was prepared as described in general procedure for nickel catalyzed ortho-C-H thiolation of N-benzoyl
α-amino derivatives. White solid, 22 mg, 34% yield (3h plus 3h’, total 80% yield). Mp: 117-120 °C.
1H NMR (500 MHz, DMSO-d6) δ 8.37 (s, 1H), 7.63 (dd, J = 7.4, 1.7 Hz, 1H), 7.46 (q, J = 4.6 Hz,
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1H), 7.42 – 7.28 (m, 7H), 7.06 (dd, J = 7.7, 1.2 Hz, 1H), 2.58 (d, J = 4.6 Hz, 3H), 1.41 (s, 6H). C
{1H} NMR (125 MHz, DMSO-d6) δ 174.2, 166.9, 137.9, 134.5, 134.3, 132.1, 130.5, 130.2, 129.6,
128.3, 127.8, 126.4, 56.5, 26.1, 25.1. LRMS (ESI) [M+H]+ found: 329.0. HRMS (ESI) [M+Na]+
calcd for C18H20O2N2NaS: 351.1138, found: 351.1139.
N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2,6-bis(phenylthio)benzamide
(3h’):
Compound 3h’ was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 66 mg, 76% yield. Mp: 174-177 °C. H
NMR (500 MHz, DMSO-d6) δ 8.70 (s, 1H), 7.44 – 7.36 (m, 8H), 7.36 – 7.29 (m, 3H), 7.23 – 7.16 (m,
3H), 2.55 (d, J = 4.7 Hz, 3H), 1.43 (s, 6H). C {1H} NMR (125 MHz, DMSO-d6) δ 174.1, 165.6,
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142.3, 134.5, 133.0, 131.8, 131.1, 130.3, 129.5, 127.7, 57.0, 25.9, 25.0. LRMS (ESI) [M+H]+ found:
436.9. HRMS (ESI) [M+Na]+ calcd for C24H24O2N2NaS2: 459.1171, found: 459.1167. Anal. Calcd for
C24H24O2N2S2: C, 66.02; H, 5.54; N, 6.42; found: C, 64.20; H, 5.38; N, 6.22.
4-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2,6-bis(phenylthio)benzamide (3i):
Compound 3i was prepared as described in general procedure for nickel catalyzed ortho-C-H
1
thiolation of N-benzoyl α-amino derivatives. White solid, 68 mg, 76% yield. Mp: 204-206 °C. H
NMR (500 MHz, DMSO-d6) δ 8.59 (s, 1H), 7.42 – 7.35 (m, 8H), 7.34 – 7.26 (m, 2H), 7.17 (q, J = 4.2
Hz, 1H), 7.10 (s, 2H), 2.52 (d, J = 4.7 Hz, 3H), 2.16 (s, 3H), 1.40 (s, 6H). 13C {1H} NMR (125 MHz,
DMSO-d6) δ 174.2, 165.8, 140.6, 140.2, 134.9, 133.0, 132.3, 130.6, 129.5, 127.5, 56.9, 25.8, 25.0,
20.4. LRMS (ESI) [M+H]+ found: 451.0. HRMS (ESI) [M+Na]+ calcd for C25H26O2N2NaS2:
473.1328, found: 473.1325.
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4-(Dimethylamino)-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2,6-
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bis(phenylthio)benzamide (3j): Compound 3j was prepared as described in general procedure for
nickel catalyzed ortho-C-H thiolation of N-benzoyl α-amino derivatives. White solid, 74 mg, 77%
yield. Mp: 188-190 °C. 1H NMR (400 MHz, DMSO-d6) δ 8.37 (s, 1H), 7.47 – 7.34 (m, 8H), 7.32 –
7.25 (m, 2H), 7.16 (q, J = 4.8 Hz, 1H), 6.56 (s, 2H), 2.74 (s, 6H), 2.51 (d, J = 4.8 Hz, 3H), 1.35 (s,
6H). 13C {1H} NMR (100 MHz, DMSO-d6) δ 174.3, 166.1, 150.6, 135.5, 132.6, 131.4, 130.1, 129.3,
127.1, 115.6, 56.7, 39.5, 25.8, 24.9. LRMS (ESI) [M+H]+ found: 480.0. HRMS (ESI) [M+Na]+ calcd
for C26H29O2N3NaS2: 502.1593, found: 502.1581.
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2,4-Dimethyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(phenylthio)benzamide (3k):
Compound 3k was prepared as described in general procedure for nickel catalyzed ortho-C-H
1
thiolation of N-benzoyl α-amino derivatives. White solid, 61 mg, 85% yield. Mp: 180-182 °C. H
NMR (500 MHz, DMSO-d6) δ 8.36 (s, 1H), 7.35 – 7.27 (m, 4H), 7.27 – 7.22 (m, 2H), 7.07 (s, 1H),
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7.00 (s, 1H), 2.55 (d, J = 4.6 Hz, 3H), 2.27 (s, 3H), 2.22 (s, 3H), 1.40 (s, 6H). C {1H} NMR (125
MHz, DMSO-d6) δ 174.2, 167.2, 138.9, 138.8, 136.2, 135.4, 131.3, 130.8, 129.8, 129.6, 129.2, 126.8,
56.5, 25.9, 25.0, 20.5, 18.6. LRMS (ESI) [M+H]+ found: 357.0. HRMS (ESI) [M+Na]+ calcd for
C20H24O2N2NaS: 379.1451, found: 379.1445.
N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2-(phenylthio)-1-naphthamide (3l): Compound
3l was prepared as described in general procedure for nickel catalyzed ortho-C-H thiolation of N-
benzoyl α-amino derivatives. White solid, 66 mg, 87% yield. Mp: 165-167 °C. 1H NMR (400 MHz,
DMSO-d6) δ 8.78 (s, 1H), 8.05 (d, J = 8.3 Hz, 1H), 8.05 (d, J = 8.3 Hz, 1H), 7.94 (d, J = 7.6 Hz, 1H),
7.67 – 7.54 (m, 2H), 7.46 (q, J = 4.8 Hz, 1H), 7.42 – 7.23 (m, 6H), 2.64 (d, J = 4.6 Hz, 3H), 1.50 (s,
6H). 13C {1H} NMR (100 MHz, DMSO-d6) δ 174.1, 166.5, 138.9, 135.4, 132.0, 130.5, 130.2, 129.5,
129.3, 128.1, 127.8, 127.4, 127.2, 126.9, 125.5, 56.8, 26.1, 25.1. LRMS (ESI) [M+H]+ found: 379.0.
HRMS (ESI) [M+Na]+ calcd for C22H22O2N2NaS: 401.1294, found: 401.1284.
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N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-3-(phenylthio)thiophene-2-carboxamide (3m):
Compound 3m was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. Colorless oil, 23 mg, 35% yield. H NMR (500 MHz,
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DMSO-d6) δ 8.52 (s, 1H), 7.77 (d, J = 5.2 Hz, 1H), 7.74 (q, J = 4.5 Hz, 1H), 7.42 – 7.29 (m, 5H), 6.86
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(d, J = 5.2 Hz, 1H), 2.60 (d, J = 4.5 Hz, 3H), 1.44 (s, 6H). C {1H} NMR (125 MHz, DMSO-d6) δ
174.1, 159.6, 136.7, 134.4, 132.0, 130.9, 130.3, 129.7, 129.6, 127.7, 56.8, 26.2, 24.6. LRMS (ESI)
[M+H]+ found: 335.0. HRMS (ESI) [M+Na]+ calcd for C16H18O2N2NaS2: 357.0702, found: 357.0692.
N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-2-(phenylthio)benzo[b]thiophene-3-
carboxamide (3n): Compound 3n was prepared as described in general procedure for nickel catalyzed
ortho-C-H thiolation of N-benzoyl α-amino derivatives. White solid, 61 mg, 79% yield. Mp: 186-
189 °C. 1H NMR (400 MHz, DMSO-d6) δ 8.52 (s, 1H), 7.95-7.89 (m, 2H), 7.53 – 7.33 (m, 8H), 2.61
(d, J = 4.6 Hz, 3H), 1.48 (s, 6H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 174.1, 162.5, 139.7, 137.5,
136.2, 135.3, 134.4, 130.7, 129.6, 128.2, 125.4, 125.1, 123.4, 122.2, 56.7, 26.2, 25.1. LRMS (ESI)
[M+H]+ found: 385.0. HRMS (ESI) [M+Na]+ calcd for C20H20N2O2NaS2: 407.0858, found: 407.0855.
2-Methyl-N-(1-(methylcarbamoyl)cyclopropyl)-6-(phenylthio)benzamide (3o): Compound 3o
was prepared as described in general procedure for nickel catalyzed ortho-C-H thiolation of N-benzoyl
α-amino derivatives. White solid, 61 mg, 90% yield. Mp: 183-186 °C. 1H NMR (500 MHz, DMSO-
d6) δ 9.05 (s, 1H), 7.38 – 7.19 (m, 9H), 2.60 (d, J = 4.8 Hz, 3H), 2.25 (s, 3H), 1.34 – 1.29 (m, 2H),
1.02 – 0.96 (m, 2H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 171.2, 168.9, 141.2, 135.7, 135.4, 131.4,
130.2, 129.8, 129.7, 129.5, 129.4, 127.0, 34.2, 26.1, 18.6, 15.7. LRMS (ESI) [M+H]+ found: 341.0.
HRMS (ESI) [M+H]+ calcd for C19H21O2N2S: 341.1318, found: 341.1315.
2-Methyl-N-(1-(methylcarbamoyl)cyclohexyl)-6-(phenylthio)benzamide (3p): Compound 3p was
prepared as described in general procedure for nickel catalyzed ortho-C-H thiolation of N-benzoyl α-
amino derivatives. White solid, 61 mg, 80% yield. Mp: 165-168 °C. 1H NMR (400 MHz, DMSO-d6)
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δ 8.30 (s, 1H), 7.37 – 7.21 (m, 8H), 7.15 (d, J = 7.3 Hz, 1H), 2.54 (d, J = 4.6 Hz, 3H), 2.36 (s, 3H),
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2.16 (s, 1H), 2.12 (s, 1H), 1.72 – 1.62 (m, 2H), 1.61 – 1.42 (m, 5H), 1.26 – 1.12 (m, 1H). C {1H}
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NMR (100 MHz, DMSO-d6) δ 174.3, 167.7, 141.7, 136.2, 135.7, 131.1, 130.3, 130.0, 129.8, 129.3,
129.2, 126.7, 60.1, 31.7, 25.8, 25.0, 21.1, 19.2. LRMS (ESI) [M+H]+ found: 383.0. HRMS (ESI)
[M+H]+ calcd for C22H27O2N2S: 383.1788, found: 383.1789. Anal. Calcd for C22H26O2N2S: C, 69.08;
H, 6.85; N, 7.32; found: C, 68.74; H, 6.91; N, 7.17.
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2-Methyl-N-(1-(methylamino)-1-oxopropan-2-yl)-6-(phenylthio)benzamide (3q): Compound 3q
was prepared as described in general procedure for nickel catalyzed ortho-C-H thiolation of N-benzoyl
α-amino derivatives. White solid, 48 mg, 73% yield. Mp: 162-164 °C. 1H NMR (500 MHz, DMSO-
d6) δ δ 8.52 (d, J = 7.5 Hz, 1H), 7.67 (q, J = 4.5 Hz, 1H), 7.36 – 7.29 (m, 4H), 7.29 – 7.22 (m, 2H),
7.20 (d, J = 7.4 Hz, 1H), 7.07 (d, J = 7.6 Hz, 1H), 4.46 – 4.37 (m, 1H), 2.59 (d, J = 4.6 Hz, 3H), 2.28
(s, 3H), 1.24 (d, J = 7.1 Hz, 3H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 172.2, 167.0, 140.8, 135.8,
135.5, 131.2, 130.5, 130.0, 129.4, 129.3, 129.2, 127.0, 48.4, 25.5, 18.9, 17.9. LRMS (ESI) [M+H]+
found: 328.9. HRMS (ESI) [M+H]+ calcd for C18H21O2N2S: 329.1318, found: 329.1317. Anal. Calcd
for C18H20O2N2S: C, 65.83; H, 6.14; N, 8.53; found: C, 66.43; H, 6.22; N, 8.33.
2-Methyl-N-(3-methyl-1-(methylamino)-1-oxobutan-2-yl)-6-(phenylthio)benzamide
(3r):
Compound 3r was prepared as described in general procedure for nickel catalyzed ortho-C-H
thiolation of N-benzoyl α-amino derivatives. White solid, 61 mg, 85% yield. Mp: 140-143 °C. [α]20
D
= -65.4 (c 0.220, MeOH). 1H NMR (500 MHz, DMSO-d6) δ 8.42 (d, J = 8.7 Hz, 1H), 7.78 (q, J = 4.6
Hz, 1H), 7.35 – 7.29 (m, 4H), 7.28 – 7.21 (m, 2H), 7.18 (d, J = 7.4 Hz, 1H), 7.05 (d, J = 7.6 Hz, 1H),
4.23 (dd, J = 8.3, 7.8 Hz, 1H), 2.59 (d, J = 4.6 Hz, 3H), 2.25 (s, 3H), 2.06 – 1.97 (m, 1H), 0.89 (d, J =
4.9 Hz, 3H), 0.88 (d, J = 4.9 Hz, 3H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 171.1, 167.5, 141.1,
136.0, 135.3, 131.3, 130.5, 130.0, 129.25, 129.21, 129.0, 127.0, 58.6, 29.9, 25.4, 19.4, 19.0, 18.5.
LRMS (ESI) [M+H]+ found: 357.0. HRMS (ESI) [M+H]+ calcd for C20H25O2N2S: 357.1631, found:
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357.1628.
2-Methyl-N-(4-methyl-1-(methylamino)-1-oxopentan-2-yl)-6-(phenylthio)benzamide
(3s):
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thiolation of N-benzoyl α-amino derivatives. White solid, 56 mg, 76% yield. Mp: 178-180 °C. H
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NMR (500 MHz, DMSO-d6) δ 8.53 (d, J = 8.1 Hz, 1H), 7.71 (q, J = 4.5 Hz, 1H), 7.34 – 7.27 (m, 4H),
7.27 – 7.22 (m, 2H), 7.20 (d, J = 7.3 Hz, 1H), 7.08 (d, J = 7.5 Hz, 1H), 4.46 – 4.37 (m, 1H), 2.57 (d,
J = 4.6 Hz, 3H), 2.27 (s, 3H), 1.76 – 1.62 (m, 1H), 1.59 – 1.50 (m, 1H), 1.44 – 1.36 (m, 1H), 0.86 (d,
J = 6.5 Hz, 3H), 0.83 (d, J = 6.6 Hz, 3H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 172.2, 167.4, 141.1,
136.0, 135.4, 130.9, 130.3, 130.2, 129.4, 129.2, 129.1, 126.9, 51.2, 40.4, 25.5, 24.1, 23.1, 21.2, 18.9.
LRMS (ESI) [M+H]+ found: 371.0. HRMS (ESI) [M+H]+ calcd for C21H27O2N2S: 371.1788, found:
371.1785.
2-Methyl-N-(1-(methylamino)-1-oxo-3-phenylpropan-2-yl)-6-(phenylthio)benzamide
(3t):
Compound 3t was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 44 mg, 54% yield. Mp: 193-195 °C. H
NMR (500 MHz, DMSO-d6) δ 8.69 (d, J = 8.3 Hz, 1H), 7.74 (q, J = 4.4 Hz, 1H), 7.40 – 7.24 (m, 7H),
7.24 – 7.14 (m, 4H), 7.11 (d, J = 7.5 Hz, 1H), 7.02 (d, J = 7.7 Hz, 1H), 4.68 (td, J = 10.4, 4.6 Hz, 1H),
3.08 (dd, J = 13.8, 4.4 Hz, 1H), 2.83 (dd, J = 13.8, 10.6 Hz, 1H), 2.58 (d, J = 4.6 Hz, 3H), 1.90 (s, 3H).
13C {1H} NMR (125 MHz, DMSO-d6) δ 171.2, 167.4, 140.6, 138.0, 135.8, 135.4, 131.4, 130.6, 129.8,
129.3, 129.2, 129.1, 128.0, 127.1, 126.2, 54.3, 37.1, 25.5, 18.4. LRMS (ESI) [M+H]+ found: 405.0.
HRMS (ESI) [M+H]+ calcd for C24H23O2N2S: 403.1486, found: 403.1495.
2-(3-Methyl-2-(2-methyl-6-(phenylthio)benzamido)butanamido)acetic acid (3u): Compound 3u
was prepared as described in general procedure for nickel catalyzed ortho-C-H thiolation of N-benzoyl
α-amino derivatives. White solid, 52 mg, 67% yield. Mp: 183-186 °C. 1H NMR (400 MHz, DMSO-
d6) δ 12.58 (br, 1H), 8.50 (s, 1H), 7.63 (t, J = 5.5 Hz, 1H), 7.36 – 7.19 (m, 7H), 7.10 (d, J = 7.4 Hz,
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1H), 3.73 (d, J = 5.5 Hz, 2H), 2.31 (s, 3H), 1.44 (s, 6H). C {1H} NMR (100 MHz, DMSO-d6) δ
174.0, 171.1, 167.2, 140.8, 135.8, 135.7, 131.0, 130.4, 129.6, 129.32, 129.26, 127.1, 56.5, 41.1, 24.8,
18.8. LRMS (ESI) [M-H]- found: 385.1. HRMS (ESI) [M+Na]+ calcd for C20H22O4N2NaS: 409.1192,
found: 409.1183.
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2-Methyl-N-(3-methyl-1-((2-(methylamino)-2-oxoethyl)amino)-1-oxobutan-2-yl)-6-(phenyl-
thio)benzamide (3v): Compound 3v was prepared as described in general procedure for nickel
catalyzed ortho-C-H thiolation of N-benzoyl α-amino derivatives. White solid, 24 mg, 30% yield. Mp:
168-172 °C. 1H NMR (400 MHz, MeOD) δ 7.41 – 7.08 (m, 8H), 3.80 (s, 2H), 2.50 (s, 3H), 2.41 (s,
3H), 1.54 (s, 6H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 173.8, 169.0, 168.3, 140.3, 135.83, 135.78,
130.9, 130.6, 129.9, 129.7, 129.5, 129.3, 126.9, 56.4, 42.9, 25.3, 24.8, 18.7. LRMS [M+H]+ found
400.0. HRMS (ESI) [M+H]+ calcd for C21H26O3N3S: 400.1689, found: 400.1679.
2-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(p-tolylthio)benzamide
(4b):
Compound 4b was prepared as described in general procedure for nickel catalyzed ortho-C-H
thiolation of N-benzoyl α-amino derivatives. White solid, 61 mg, 85% yield. Mp: 98-102 °C. 1H NMR
(400 MHz, DMSO-d6) δ 8.50 (s, 1H), 7.38 – 7.12 (m, 7H), 7.02 (d, J = 7.5 Hz, 1H), 2.57 (d, J = 4.4
Hz, 3H), 2.29 (s, 3H), 2.28 (s, 3H), 1.43 (s, 6H). 13C {1H} NMR (150 MHz, DMSO-d6) δ 174.2, 167.1,
140.3, 137.2, 135.4, 132.0, 131.6, 131.4, 130.1, 129.5, 129.2, 129.1, 56.6, 26.0, 25.0, 20.6, 18.7.
LRMS (ESI) [M+H]+ found: 357.0. HRMS (ESI) [M+Na]+ calcd for C20H24O2N2NaS: 379.1451,
found: 379.1440.
2-((4-Methoxyphenyl)thio)-6-methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-
yl)benzamide (4c): Compound 4c was prepared as described in general procedure for nickel catalyzed
ortho-C-H thiolation of N-benzoyl α-amino derivatives. White solid, 60 mg, 81% yield. Mp: 88-91 °C.
1H NMR (500 MHz, DMSO-d6) δ 8.51 (s, 1H), 7.44 – 7.38 (m, 2H), 7.34 (q, J = 4.3 Hz, 1H), 7.21 –
7.16 (m, 1H), 7.11 (d, J = 7.5 Hz, 1H), 7.00 – 6.94 (m, 2H), 6.91 (d, J = 7.8 Hz, 1H), 3.76 (s, 3H),
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2.60 (d, J = 4.7 Hz, 3H), 2.28 (s, 3H), 1.46 (s, 6H). C {1H} NMR (125 MHz, DMSO-d6) δ 174.2,
167.1, 159.5, 139.1, 135.1, 134.7, 133.8, 129.0, 128.4, 128.0, 124.4, 115.2, 56.6, 55.3, 26.0, 25.0, 18.6.
LRMS (ESI) [M+H]+ found: 373.0. HRMS (ESI) [M+Na]+ calcd for C20H24O3N2NaS: 395.1400,
found: 395.1389.
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2-((4-Chlorophenyl)thio)-6-methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)benzamide
(4d): Compound 4d was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 74 mg, 98% yield. Mp: 173-176 °C. H
NMR (400 MHz, DMSO-d6) δ 8.48 (s, 1H), 7.41 – 7.36 (m, 2H), 7.33 – 7.23 (m, 5H), 7.19 (dd, J =
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7.3, 1.2 Hz, 1H), 2.56 (d, J = 4.7 Hz, 3H), 2.31 (s, 3H), 1.40 (s, 6H). C {1H} NMR (150 MHz,
DMSO-d6) δ 174.1, 166.9, 141.7, 135.8, 135.4, 131.6, 131.3, 131.2, 130.3, 129.6, 129.4, 129.2, 56.5,
26.0, 25.0, 18.7. LRMS (ESI) [M+H]+ found: 377.0. HRMS (ESI) [M+Na]+ calcd for
C19H21O2N2ClNaS: 399.0904, found: 399.0897.
2-((4-Fluorophenyl)thio)-6-methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)benzamide
(4e): Compound 4e was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 61 mg, 85% yield. Mp: 138-140 °C. H
NMR (600 MHz, DMSO-d6) δ 8.51 (s, 1H), 7.41 (dd, J = 8.6, 5.3 Hz, 2H), 7.30 (q, J = 4.6 Hz, 1H),
7.27 – 7.23 (m, 1H), 7.23 – 7.18 (m, 3H), 7.09 (d, J = 7.7 Hz, 1H), 2.58 (d, J = 4.6 Hz, 3H), 2.30 (s,
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3H), 1.43 (s, 6H). C {1H} NMR (150 MHz, DMSO-d6) δ 174.1, 167.0, 161.6 (d, J = 245.4 Hz),
140.7, 135.6, 133.3 (d, J = 8.3 Hz), 131.3, 131.0 (d, J = 2.9 Hz), 130.1, 129.6, 129.3, 116.4 (d, J =
23.4 Hz), 56.6, 26.0, 25.0, 18.7. LRMS (ESI) [M+H]+ found: 361.0. HRMS (ESI) [M+Na]+ calcd for
C19H21O2N2FNaS: 383.1200, found: 383.1190.
2-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(m-tolylthio)benzamide
(4f):
Compound 4f was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 59 mg, 83% yield. Mp: 156-158 °C. H
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NMR (400 MHz, DMSO-d6) δ 8.46 (s, 1H), 7.30 – 7.15 (m, 5H), 7.15 – 7.04 (m, 3H), 2.57 (d, J = 4.5
Hz, 3H), 2.30 (s, 3H), 2.26 (s, 3H), 1.41 (s, 6H). 13C {1H} NMR (150 MHz, DMSO-d6) δ 174.6, 167.5,
141.4, 139.2, 136.0, 135.8, 131.4, 131.2, 130.9, 130.1, 129.7, 128.4, 128.0, 57.0, 26.5, 25.5, 21.3, 19.2.
LRMS (ESI) [M+H]+ found: 357.0. HRMS (ESI) [M+Na]+ calcd for C20H24O2N2NaS: 379.1451,
found: 379.1444.
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2-((3-Fluorophenyl)thio)-6-methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)benzamide
(4g): Compound 4g was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 68 mg, 94% yield. Mp: 177-180 °C. H
NMR (500 MHz, DMSO-d6) δ 8.46 (s, 1H), 7.38 – 7.29 (m, 3H), 7.27 (dd, J = 7.1, 1.4 Hz, 1H), 7.22
(q, J = 4.6 Hz, 1H), 7.09 (d, J = 7.9 Hz, 1H), 7.04 (ddd, J = 17.4, 9.1, 2.1 Hz, 2H), 2.56 (d, J = 4.6 Hz,
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3H), 2.32 (s, 3H), 1.39 (s, 6H). C {1H} NMR (125 MHz, DMSO-d6) δ 174.1, 166.9, 162.3 (d, J =
246.5 Hz), 142.2, 139.4 (d, J = 7.9 Hz), 135.9, 132.1, 130.9 (d, J = 8.7 Hz), 130.8, 129.5, 128.6, 124.8,
115.4 (d, J = 23.6 Hz), 113.4 (d, J = 21.2 Hz), 56.5, 26.0, 24.9, 18.7. LRMS (ESI) [M+H]+ found:
361.0. HRMS (ESI) [M+Na]+ calcd for C19H21O2N2FNaS: 383.1200, found: 383.1191.
2-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-((3-nitrophenyl)thio)benzamide
(4h): Compound 4h was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 33 mg, 43% yield. Mp: 202-204 °C. H
NMR (500 MHz, DMSO-d6) δ 8.46 (s, 1H), 8.03 (ddd, J = 8.1, 2.2, 1.0 Hz, 1H), 7.95 – 7.92 (m, 1H),
7.65 (ddd, J = 8.1, 1.6, 1.1 Hz, 1H), 7.61 – 7.56 (m, 1H), 7.41 – 7.34 (m, 3H), 7.24 (q, J = 4.6 Hz, 1H),
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2.56 (d, J = 4.6 Hz, 3H), 2.34 (s, 3H), 1.38 (s, 6H). C {1H} NMR (125 MHz, DMSO-d6) δ 174.0,
166.7, 148.2, 142.6, 139.8, 136.18, 134.4, 132.4, 131.3, 130.4, 129.7, 127.6, 122.3, 121.1, 56.5, 26.0,
24.9, 18.8. LRMS (ESI) [M+H]+ found: 388.0. HRMS (ESI) [M+Na]+ calcd for C19H21O4N3NaS:
410.1145, found: 410.1133.
2-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(o-tolylthio)benzamide
(4i):
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Compound 4i was prepared as described in general procedure for nickel catalyzed ortho-C-H
thiolation of N-benzoyl α-amino derivatives. White solid, 51 mg, 71% yield. Mp: 91-94 °C. 1H NMR
(500 MHz, DMSO-d6) δ 8.39 (s, 1H), 7.29 (d, J = 7.3 Hz, 1H), 7.27 – 7.20 (m, 3H), 7.20 – 7.15 (m,
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{1H} NMR (125 MHz, DMSO-d6) δ 174.1, 166.9, 140.1, 138.1, 135.5, 134.1, 131.7, 131.1, 130.5,
129.2, 129.1, 128.8, 127.6, 126.9, 56.5, 25.9, 24.9, 20.0, 18.7. LRMS (ESI) [M+H]+ found: 357.0.
HRMS (ESI) [M+Na]+ calcd for C20H24O2N2NaS: 379.1451, found: 379.1441.
2-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(pyridin-2-ylthio)benzamide (4j):
Compound 4j was prepared as described in general procedure for nickel catalyzed ortho-C-H
thiolation of N-benzoyl α-amino derivatives. White solid, 49 mg, 72% yield. Mp: 84-87 °C. 1H NMR
(500 MHz, DMSO-d6) δ 8.37 (d, J = 3.9 Hz, 1H), 8.26 (s, 1H), 7.64 (ddd, J = 10.8, 4.5 Hz, 1.4 Hz
1H), 7.50 – 7.44 (m, 1H), 7.43 – 7.37 (m, 2H), 7.24 (q, J = 4.4 Hz, 1H), 7.14 (dd, J = 6.9, 5.1 Hz, 1H),
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6.93 (d, J = 8.1 Hz, 1H), 2.55 (d, J = 4.6 Hz, 3H), 2.32 (s, 3H), 1.31 (s, 6H). C {1H} NMR (125
MHz, DMSO-d6) δ 174.0, 166.8, 160.1, 149.2, 143.4, 137.4, 136.1, 134.0, 131.6, 129.5, 125.9, 121.4,
120.4, 56.4, 26.0, 24.8, 18.8. LRMS (ESI) [M+H]+ found: 344.0. HRMS (ESI) [M+Na]+ calcd for
C18H21O2N3NaS: 366.1247, found: 366.1238.
2-Methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-yl)-6-(phenylselanyl)benzamide (4k):
Compound 4k was prepared as described in general procedure for nickel catalyzed ortho-C-H
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thiolation of N-benzoyl α-amino derivatives. White solid, 45 mg, 58% yield. Mp: 107-109 °C. H
NMR (500 MHz, DMSO-d6) δ 8.44 (s, 1H), 7.49 (br, 2H), 7.32 (br, 4H), 7.27 -7.12 (m, 3H), 2.60 (d,
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J = 3.9 Hz, 3H), 2.31 (s, 3H), 1.44 (s, 6H). C {1H} NMR (125 MHz, DMSO-d6) δ 174.1, 167.5,
141.2, 135.5, 132.9, 131.4, 130.8, 129.5, 129.3, 127.7, 127.6, 56.6, 25.9, 25.0, 19.0. LRMS (ESI)
[M+H]+ found: 390.9. HRMS (ESI) [M+Na]+ calcd for C19H22O2N2NaSe: 413.0739, found: 413.0728.
2-((3-Methoxyphenyl)selanyl)-6-methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-
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yl)benzamide (4l): Compound 4l was prepared as described in general procedure for nickel catalyzed
ortho-C-H thiolation of N-benzoyl α-amino derivatives. White solid, 45 mg, 54% yield. Mp: 144-
147 °C. 1H NMR (500 MHz, CDCl3) δ 7.35 (dd, J = 6.5, 2.1 Hz, 1H), 7.22 – 7.15 (m, 3H), 7.08 (s,
1H), 6.94 – 6.89 (m, 2H), 6.80 – 6.76 (m, 1H), 5.95 (s, 1H), 3.75 (s, 3H), 2.82 (d, J = 4.8 Hz, 3H),
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2.37 (s, 3H), 1.52 (s, 6H). C {1H} NMR (125 MHz, CDCl3) δ 174.5, 168.8, 160.4, 141.3, 136.3,
133.6, 132.9, 130.8, 130.6, 130.0, 126.2, 123.9, 117.3, 113.1, 58.3, 55.5, 26.5, 25.5, 19.5. LRMS (ESI)
[M+H]+ found: 420.9. HRMS (ESI) [M-H]- calcd for C20H23O3N2Se: 419.0879, found: 419.0833.
2-((4-Chlorophenyl)selanyl)-6-methyl-N-(2-methyl-1-(methylamino)-1-oxopropan-2-
yl)benzamide (4m): Compound 4m was prepared as described in general procedure for nickel
catalyzed ortho-C-H thiolation of N-benzoyl α-amino derivatives. White solid, 36 mg, 42% yield. Mp:
86-89 °C. 1H NMR (500 MHz, DMSO-d6) δ 8.45 (s, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.1
Hz, 2H), 7.31 (d, J = 3.6 Hz, 1H), 7.26 -7.18 (m, 3H), 2.60 (d, J = 4.0 Hz, 3H), 2.32 (s, 3H), 1.43 (s,
6H). 13C {1H} NMR (125 MHz, DMSO-d6) δ 174.0, 167.5, 141.6, 135.6, 134.2, 132.4, 131.9, 130.0,
129.9, 129.44, 129.38, 126.9, 56.6, 26.0, 25.0, 19.0. LRMS (ESI) [M+H]+ found: 424.9. HRMS (ESI)
[M-H]- calcd for C19H20O2N2ClSe: 423.0384, found: 423.0386.
Author Information
Corresponding Author
E-mail: hliu@simm.ac.cn
Notes
The authors declare no competing financial interests.
Acknowledgements
F.G., W.Z., D.Z., S.L., J.W., and H.L. received funding from the National Natural Science Foundation
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of China (91229204, 21632008, and 81620108027), the Major Project of Chinese National Programs
for Fundamental Research and Development (2015CB910304), and National S&T Major Projects
(2013ZX09507-001 and 2014ZX09507002-001).
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Associated Content
Supporting Information
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Copies of H and C NMR spectra, LC/MS and HPLC experiments data. This material is available
free of charge via the Internet at http://pubs.acs.org.
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Wang, B.; Yao, J.; Zhang, Y. Org. Lett. 2015, 17, 1328-1331; (d) Yan, S. Y.; Liu, Y. J.; Liu, B.; Liu, Y.
H.; Shi, B. F. Chem. Commun. 2015, 51, 4069-4072; (e) Yang, K.; Wang, Y.; Chen, X.; Kadi, A. A.;
Fun, H. K.; Sun, H.; Zhang, Y.; Lu, H.; Chem. Commun. 2015, 51, 3582-3585; (f) Ye, X.; Petersen, J.
L.; Shi, X. Chem. Commun. 2015, 51, 7863-7866; (g) Lin, C.; Yu, W.; Yao, J.; Wang, B.; Liu, Z.;
Zhang, Y. Org. Lett. 2015, 17, 1340-1343; (h) Wang, X.; Qiu, R.; Yan, C.; Reddy, V. P.; Zhu, L.; Xu,
X.; Yin, S. F. Org. Lett. 2015, 17, 1970-1973; (i) Yan, S. Y.; Liu, Y. J.; Liu, B.; Liu, Y. H.; Zhang, Z.
Z.; Shi, B. F. Chem. Commun. 2015, 51, 7341-7344.
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