Palladium-Catalyzed Decarboxylative ortho-C(sp2)?H Aroylation of N-Sulfoximine Benzamides at Room Temperature

Article abstract of DOI:10.1002/asia.201901759

A palladium-catalyzed method for the decarboxylative ortho C?H acylation of N-sulfoximine benzamides is developed at room temperature. The catalytic method enables easy access to various functionalized 2-aroylaromatic carboxylic acid derivatives in good isolated yields. Based on our mechanistic studies, a Pd(II)/Pd(IV) catalytic cycle that involves aroyl radical intermediate is proposed for the reaction.

Full text of DOI:10.1002/asia.201901759

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Pd-catalyzed decarboxylative ortho C(sp2)-H aroylation of N-
sulfoximine benzamides at room temperature Prasenjit Das,
Promita Biswas and Joyram Guin*[a]
Authors: Prasenjit Das, Promita Biswas, and Joyram Guin
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10.1002/asia.201901759
Chemistry - An Asian Journal
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Pd-catalyzed decarboxylative ortho C(sp2)-H aroylation of N-
sulfoximine benzamides at room temperature
Prasenjit Das, Promita Biswas and Joyram Guin*[a]
Abstract: A Pd-catalyzed method for the decarboxylative ortho C-H
acylation of N-sulfoximine benzamides is developed at room
temperature. The catalytic method enables easy access to various
functionalized 2-aroylaromatic carboxylic acid derivatives in good
isolated yields. Based on our mechanistic studies, a Pd(II)/Pd(IV)
catalytic cycle that involves aroyl radical intermediate is proposed for
the reaction.
and α-oxocarboxylate salts has been first reported by the
research group of Gooßen to afford aryl ketone.[5] Subsequently,
Pd-catalyzed directing group assisted ortho C-H acylation of
acetanilides[6] and phenylpyridines[7] using α-oxocarboxylic acids
has been developed under oxidative conditions. Followed by
these works, several other directing groups including oxime,[8]
azo,[9] acetamide,[10] indole,
and others[12] have been utilized
[11]
in the decarboxylative C−H acylation of arene with α-
oxocarboxylic acids. Despite these reports, the synthesis of 2-
acylaromatic acids using oxidative Pd-catalyzed decarboxylative
ortho C-H acylation of aromatic carboxylic acid derivatives
remains relatively unexplored. In 2013, Ge et al. reported the
Pd-catalyzed decarboxylative ortho acylation of benzoic acid
using excess amount of expensive silver salt at elevated
reaction temperature (150 °C).[13] Very recently, the research
groups of Laha[14] and Wang[15] independently disclosed Pd-
catalyzed decarboxylative ortho-acylation of tertiary benzamides
using persulfate as oxidant. These reactions were performed at
high temperature (70-80 °C) and some cases a strong acid
additive was employed. Herein, we like to disclose our result on
the Pd(II)-catalyzed decarboxylative ortho C-H acylation of N-
sulfoximine benzamides under oxidative condition. The catalytic
method enables easy access to 2-aroylaromatic acid derivatives
in good isolated yield at room temperature without the need of
any additive.
Aromatic carboxylic acids possessing carbonyl group at ortho to
acid unit are found in many important biologically active natural
products and molecules (Fig. 1).[1] Furthermore, they serve as
versatile precursors to numerous heterocycles of significance
medicinal relevance.[2] Traditional synthesis of such molecules
involves either opening of 1,3-isobenzofurandione derivatives
with excess organometallic reagents via addition/elimination
process or Lewis acid mediated Friedel-Crafts acylation
3]
reaction.[1b,
However, the utilization of these conventional
syntheses of 2-acyl/aroyl aromatic carboxylic acids are limited
due to several disadvantages like a) the requirement of a
stoichiometric amount of organometallic reagent/Lewis acid, b)
poor functional group tolerance and c) low regioselectivity, Thus,
the development of a more convenient approach to such target
is highly desirable.
Figure 1. Some natural products containing 2-aroylbenzoic acid structural unit
and some medicinally important heterocycles derived from 2-aroylbenzoic acid.
Scheme 1. Previously reported methods and this work for the Pd(II)-catalyzed
decarboxylative ortho C-H aroylation of aromatic carboxylic acid derivatives.
Recently,
transition-metal-catalyzed
decarboxylative
acylation of arene has emerged as an effective tool for the
synthesis of acylated aromatic compound.[4] Pd-catalyzed
decarboxylative cross-coupling reaction between aryl bromides
Sulfoximine structural units have attracted much attention in
agriculture sciences[16] and medicinal chemistry.[17] Furthermore,
sulfoximines have recently been recognised as an effective and
reusable directing group for transition metal catalyzed
functionalization of unactivated C-H bonds.[18] Indeed, different
functional groups such as alkyl, amide, acetoxyl, hydroxyl,
halide etc. have been introduced at C-H bond using sulfoximine
assisted transition metal catalysis.[19] Nevertheless, the
installation of acyl/aroyl moiety at arene C-H bond of N-
sulfoximine benzamide has not been reported. In light with
[a]
P. Das, P. Biswas and Dr. J. Guin*
School of Chemical Sciences
Indian Association for the Cultivation of Science
2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata-700032 (India)
E-mail: ocjg@iacs.res.in
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/asia.201901759
Chemistry - An Asian Journal
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immense biological as well as synthetic relevance of sulfoximine
moiety and 2-aroylaromatic carboxylic acid derivatives, we
became interested in developing a method for decarboxylative
ortho C-H aroylation of N-sulfoximine benzamides using
oxidative Pd-catalysis.
benzamide (1a) using phenylglyoxalic acid (2a) as aroyl coupling
partner, Pd(OAc)2 (5 mol%) as catalysts in air at 25 °C in DCE
(Table 1). The reaction resulted in a very low GC-conversion
(20% of the product 3a) of 1a to the desired product 3a (entry 1).
A slight improved reactivity on the catalytic benzoylation reaction
was realized, when O2-balloon was used (entry 2). While this
result proved the feasibility of developing an aerobic method for
the decarboxylative ortho C-H benzoylation of N-sulfoximine
benzamides, the reaction efficacy could not be improved further
using O2 as the sole oxidant. Following the literature report, we
then decided to develop the reaction using ammonium
persulfate as oxidant. Effect of solvent in the catalytic process
was then undertaken. With polar non-coordinating solvents, like
DCE and EtOAc, the reaction exhibited moderate reactivity
towards the desired product formation (entries 3 and 4). Poor
solubility of ammonium persulfate in those solvents at room
temperature may be responsible for such observation. The
conversion of the amide 1a to the ortho benzoylated product 3a
was significantly improved upon carrying out the reaction in
polar coordinating solvents such as DME, mixture of DME and
acetic acid (1:1 v/v) or diglyme (entries 5-7). Finally, diglyme was
identified as the superior solvent for the catalytic reaction. Other
oxidant like K2S2O8 and PIDA did not improve the reaction
efficacy (entries 8 and 9). Other common Pd(II)-salts were also
tested in this reaction, which afforded the desired product either
in similar or low GC-conversion than that of the Pd(OAc)2
(entries 10 and 11). Increasing the loading of Pd(OAc)2 to 10
mol%, slight improvement on the conversion of 1a to the product
3a was observed (entry 12). Further optimization studies were
conducted with varying concentration of 1a in the reaction
mixture (entries 12-14; see Supporting Information). Finally, the
optimized reaction conditions including 1a (1 equiv),
phenylglyoxalic acid (3 equiv), (NH4)2S2O8 (2 equiv), 10 mol% of
Pd(OAc)2 in 0.07 M reaction concentration with respect to 1a
afforded the product 3a in 73% isolated yield (entry 13). Control
experiments confirmed that the reaction did not afford the
desired product in the absence of either palladium catalyst or
oxidant (entries 15 and 16).
Having established the optimal reaction conditions for the
catalytic decarboxylative ortho C-H aroylation process, we
decided to explore scope and limitation of the reaction with
varying reaction partners (Table 2). At the beginning, we
performed the reaction using different N-sulfoximine benzamides
varying substituents at the aromatic ring of benzamide unit with
phenylglyoxalic acid. Accordingly, N-sulfoximine benzamide as
well as its ortho-, meta-, and para-methyl derivatives were
transformed to the corresponding ortho-benzoylated products
3a-d in good yields (71-83%). The reaction afforded product 3e
in equal efficiency with the substrate having bulky tert-butyl
group. Products possessing electron rich methoxy (3f and 3g),
benzyloxy (3h) substituents at benzamide unit were synthesized
in good yields. Substrates containing halides (Cl and Br)
functionality at benzamide moiety exhibited sluggish reactivity
towards the catalytic C-H aroylation reaction. They required
slightly higher reaction temperature (80 °C) to furnish the
desired products 3i-k in acceptable isolated yields. Furthermore,
substrates having strong electron withdrawing groups such as
Results and Discussion
At present, our group has been actively working on the
development of novel oxidative organic transformations using
molecular oxygen as the sole oxidant/reagent.[20] Along with this
line, we have recently introduced a new reaction protocol for the
Pd(II)-catalyzed direct C-H hydroxylation of arene using
molecular oxygen.[21] Inspired by our earlier work, we began our
studies towards the development of Pd(II)-catalyzed
decarboxylative ortho C-H aroylation of N-sulfoximine
Table 1. Reaction optimization.[a]
Entry
1[c]
2[c]
3
Cat. (mol%)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Oxidant
air
Solvent
DCE
3a (%)[b]
20
O2-balloon
(NH4)2S2O8
(NH4)2S2O8
(NH4)2S2O8
(NH4)2S2O8
DCE
41
DCE
52
4
EtOAc
DME
50
5
65
6
DME:AcOH
(1:1)
67
7
8
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(TFA)2 (5)
Pd(ACN)2Cl2 (5)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
-
(NH4)2S2O8
K2S2O8
diglyme
diglyme
diglyme
diglyme
diglyme
diglyme
diglyme
diglyme
diglyme
diglyme
69
59
9
PIDA
30
10
(NH4)2S2O8
(NH4)2S2O8
(NH4)2S2O8
(NH4)2S2O8
(NH4)2S2O8
(NH4)2S2O8
-
65
11
33
12[d]
13[d]
14[d]
15
72
80 (73)
39
-
16
Pd(OAc)2 (10)
-
[a] Reaction conditions: 1a (1.0 equiv), 2a (3.0 equiv), oxidant (2.0 equiv.),
catalyst, in different solvent at 25 °C under argon atmosphere (balloon) for 24
h. [b] Reaction conversion determined by GC analysis, isolated yields is given
in parenthesis. [c] Reaction performed under aerobic condition, [d] Reaction
performed varying reaction concentration with respect to 1a.
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10.1002/asia.201901759
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Table 2. Substrate scope.[a]
electron rich (OMe) substituents at aromatic ring of the
sulfoximine unit furnishing desired ortho-benzoylated products
3o-s in good isolated yields. The products 3t and 3u having
ethyl and diphenyl sulfoximine moieties, respectively were
synthesized in good to moderate yields with this protocol.
Increasing steric congestion around sulfoximine centre may be
responsible for low yield of the product 3u. The versatility of this
transformation was then evaluated with different functionalized
acid coupling partners. With this method, ortho benzoylated
products 3v-x having 4-chloro, 4-methyl and 3,4-dimethoxy
substituents at benzoyl unit were synthesized in good isolated
yields. Notably, the formation of bis-benzoylated product under
the optimized reaction conditions was not realized.
A preparative scale experiment was carried out to establish
synthetic usefulness of the method. Under the optimized
reaction conditions, the title reaction worked well with 1 g of
substrate 1a to afford 0.926 g of 3a with 66% yield (Scheme 2).
Furthermore, the removal of sulfoximine directing group and
synthesis of different 6-/5-membered heterocyclic compounds of
high medicinal relevance were achieved by carrying out simple
chemical transformations using the product 3a. Accordingly, the
substituted nitrogen containing heteroaromatic compounds 4
and 5 were synthesized in good yields upon treatment with
hydroxylamide and hydrazine hydrate, respectively. NaBH4
reduction of the product 3a resulted in good yield of the
substituted lactone 6. The synthesis of the functionalized lactam
7 was completed from 3a in good yield (Scheme 2). Notably, in
all cases, the sulfoximine directing group was recovered in good
amount that could be reused for the synthesis of the substrate.
[a] Reaction conditions: sulfoximine amides (1.0 equiv), acids (3.0 equiv),
oxidant (2.0 equiv.), Pd(OAc)2 (10 mol%) and diglyme at rt for 24 h; isolated
yields [b] Reaction performed at 80 °C for 36 h.
Scheme 2. Post-modification of the product 3a.
The sulfoximine directing group could also be removed from the
product via acid hydrolysis, enabling the synthesis of
nitro, cyano, keto and ester in amide ring found to be ineffective
with this protocol. Substrate scope studies were then continued
with varying substituent in both the aromatic rings of sulfoximine
amide (Table 2). N-Sulfoximine benzamides bearing alkyl
substituents like di-methyl, iso-propyl, tert-butyl on the
sulfoximine aromatic ring afforded the products 3l-n in moderate
to good yields. The reaction exhibited similar reactivity with
substrates having electron deficient (F, Cl, NO2) as well as
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10.1002/asia.201901759
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2-benzoylbenzoic acid 8 in 77% yield along with the recovery of
sulfoximine directing group in 71% yield (Eq. 1).
confirm the involvement of aroyl radical in this process, the
reaction was carried out in the presence of radical scavenger
like TEMPO. As expected, no desired ortho benzoylated product
formation was noticed when the reaction was performed in the
presence of 3 equivalents of TMEPO otherwise under the
optimized reaction conditions. On the contrary, the formation of
TEMPO-ester was realized (Eq. 6). This indicates the generation
of aroyl radical via decarboxylation of α-oxocarboxylic acid.
The title reaction was then performed using enantioenriched
N-sulfoximine benzamide 1a-ent as substrate. With our
expectation, the reaction afforded the desired 2-benzoylated
product 3a-ent in good yield with no loss of enantioselectivity
(Eq. 2). However, attempt to obtain enantioenriched
benzolactone
via
stereoselective
reduction
of
the
enantioenriched ketone was unsuccessful.
We then performed a series of other experiments to shed
light into the reaction mechanism of the catalytic decarboxylative
C-H aroylation process. Accordingly, electronically non-
equivalent substrates were subjected to the catalytic reaction,
which clearly indicates a strong preference of C-H benzoylation
of electron-rich substrate over the electron-deficient amide (Eq.
3). Kinetic isotope experiment was then carried out using
Following the results obtained in our preliminary mechanistic
studies and literature reports, a probable reaction mechanism for
the Pd-catalyzed C-H aroylation process is presented in Scheme
3. The catalytic cycle involves sulfoximine assisted ortho C-H
palladation of aromatic acid unit. Meanwhile, decarboxylation of
α-oxocarboxylic acid produces the reactive aroyl radical
intermediate. The addition of the in situ generated radical
intermediate to the palladacycle followed by single electron
oxidation may lead to a PdIV-intermediate. Through a reductive
elimination process, the putative PdIV-species is expected to
deliver the desired ortho-aroylated product and regenerate the
catalyst. However, a binuclear PdII/PdIII catalytic cycle may also
be operated in the catalytic process.[23]
N-sulfoximine amide 1a and its deuterated analogue. A sluggish
reactivity with perdeuterated amide was observed when the
catalytic reaction was conducted separately using 1a and 1a(d5)
otherwise identical reaction conditions. Further studies to
determine Kinetic Isotope Effect (KIE) of the Pd-catalyzed
reaction were performed using the amides 1a(d5) and 1a(d1).
Accordingly, the reaction afforded kH/kD = 3.18 for intramolecular
(Eq. 4) and kH/kD = 2.02 for intermolecular study (Eq. 5). These
observations may suggest that the Pd-catalyzed C−H metalation
step of the reaction is most likely to be the rate-limiting step of
the process. [22]
Scheme 3. Proposed reaction mechanism.
Conclusions:
In summary, the first example of Pd-catalyzed ortho C-H
aroylation of arene using sulfoximine as reusable directing group
is developed. The reaction proceeds via oxidative
decarboxylation of α-oxocarboxylic acid at room temperature.
The catalytic process enables synthesis of various 2-
aroylbenzoic acid derivatives in good yields and functional group
The α-oxocarboxylic acids are expected to be the precursors
of aroyl radicals for the Pd-catalyzed C-H aroylation reaction. To
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10.1002/asia.201901759
Chemistry - An Asian Journal
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[3] a) H. Yu, Y. Xiao, H. Guo, Org. Lett. 2012, 14, 2014; b) S. Seo, M. Slater,
M. F. Greaney, Org. Lett. 2012, 14, 2650; c) X. Wang, J. Li, N. Zhao, X. Wan,
Org. Lett. 2011, 13, 709; d) H. Reinheckel, K. Haage, Angew. Chem. Int. Ed.
1966, 5, 511; e) J. A. LaBudde, C. Heidelberger, J. Am. Chem. Soc. 1958, 80,
1225; f) M. S. Newman, P. G. Scheurer, J. Am. Chem. Soc. 1956, 78, 5004; g)
M. S. Newman, C. W. Muth, J. Am. Chem. Soc. 1950, 72, 5191; h) L. F. Fieser,
E. B. Hershberg, J. Am. Chem. Soc. 1937, 59, 2331.
tolerance. Based on our mechanistic studies, a Pd(II)/Pd(IV)
catalytic cycle is suggested for the sulfoximine directed ortho C-
H aroylation of aromatic acid derivatives.
Experimental Section
[4] a) S. Arshadi, S. Ebrahimiasl, A. Hosseinian, A. Monfared, E. Vessally,
RSC Adv. 2019, 9, 8964; b) T. Zhang, N.-X. Wang, Y. Xing, J. Org. Chem.
2018, 83, 7559; c) T. Patra, D. Maiti, Chem. Eur. J. 2017, 23, 7382; d) A.
Fromm, C. van Wüllen, D. Hackenberger, L. J. Gooßen, J. Am. Chem. Soc.
2014, 136, 10007; e) R. Shang, L. Liu, Science China Chem. 2011, 54, 1670;
f) N. Rodríguez, L. J. Goossen, Chem. Soc. Rev. 2011, 40, 5030.
[5] a) L. J. Gooßen, F. Rudolphi, C. Oppel, N. Rodríguez, Angew. Chem. Int.
Ed. 2008, 47, 3043; b) L. J. Gooßen, G. Deng, L. M. Levy, Science 2006, 313,
662.
General Procedure I
To an oven dried 10 mL Schlenk tube equipped with a magnetic stir bar,
Pd(OAc)2 (10 mol%), substrate (1.0 equiv) and ammonium persulfate
(2.0 equiv) in diglyme (0.07 M) were placed. The resulting solution was
then freeze thaw and backfill with argon for three times prior to the
addition of α-oxocarboxylic acids (3.0 equiv) to the solution. The reaction
flask was then stirred at room temperature under argon (balloon)
atmosphere for 24 h. The progress of the reaction was monitored by TLC
analysis. After running the reaction to an appropriate time (exact reaction
time is specified in the individual experiment, see Supporting Information),
the reaction mixture was allowed to cool to room temperature and
concentrated under reduced pressure. The crude material was purified
by column chromatography on silica gel to afford the desired product.
[6] a) C. Zhou, P. Li, X. Zhu, L. Wang, Org. Lett. 2015, 17, 6198; b) P. Fang, M.
Li, H. Ge, J. Am. Chem. Soc. 2010, 132, 11898.
[7] M. Li, H. Ge, Org. Lett. 2010, 12, 3464.
[8] a) Z. Yang, X. Chen, J. Liu, Q. Gui, K. Xie, M. Li, Z. Tan, Chem. Commun.
2013, 49, 1560; b) M. Kim, J. Park, S. Sharma, A. Kim, E. Park, J. H. Kwak, Y.
H. Jung, I. S. Kim, Chem. Commun. 2013, 49, 925.
[9] a) Z.-Y. Li, D.-D. Li, G.-W. Wang, J. Org. Chem. 2013, 78, 10414; b) H. Li,
P. Li, H. Tan, L. Wang, Chem. Eur. J. 2013, 19, 14432; c) N. Xu, P. Li, Z. Xie,
L. Wang, Chem. Eur. J. 2016, 22, 2236.
Acknowledgements
[10] J. Park, M. Kim, S. Sharma, E. Park, A. Kim, S. H. Lee, J. H. Kwak, Y. H.
Jung, I. S. Kim, Chem. Commun. 2013, 49, 1654.
[11] a) J. Zhang, M. Wu, J. Fan, Q. Xu, M. Xie, Chem. Commun. 2019, 55,
8102; b) M. Kim, N. Kumar Mishra, J. Park, S. Han, Y. Shin, S. Sharma, Y.
Lee, E.-K. Lee, J. H. Kwak, I. S. Kim, Chem. Commun. 2014, 50, 14249; c) C.
Pan, H. Jin, X. Liu, Y. Cheng, C. Zhu, Chem. Commun. 2013, 49, 2933.
[12] a) P.-Y. Lee, P. Liang, W.-Y. Yu, Org. Lett. 2017, 19, 2082; b) Y. Wu, L.
Sun, Y. Chen, Q. Zhou, J.-W. Huang, H. Miao, H.-B. Luo, J. Org. Chem. 2016,
81, 1244; c) B. Majhi, D. Kundu, T. Ghosh, B. C. Ranu, Adv. Synth. Catal.
2016, 358, 283; d) L. Han, Y. Wang, H. Song, H. Han, L. Wang, W. Chu, Z.
Sun, RSC Adv. 2016, 6, 20637; e) B. Xu, W. Liu, C. Kuang, Euro. J.Org.
Chem. 2014, 2014, 2576; f) J. Yao, R. Feng, Z. Wu, Z. Liu, Y. Zhang, Adv.
Synth. Catal. 2013, 355, 1517; g) S. Sharma, A. Kim, E. Park, J. Park, M. Kim,
J. H. Kwak, S. H. Lee, Y. H. Jung, I. S. Kim, Adv. Synth. Catal. 2013, 355,
667; h) H. Li, P. Li, Q. Zhao, L. Wang, Chem. Commun. 2013, 49, 9170; i) H.
Wang, L.-N. Guo, X.-H. Duan, Org. Lett. 2012, 14, 4358.
We gratefully acknowledge the generous financial support from
Science
and
Engineering
Research
Board,
India
(TAR/2018/000075 and EMR/2016/006344) and CSIR for
fellowship to PD and PB. We sincerely thank Dr. D. Saha for
helping with the prepration of the manuscript.
Keywords: Ambient conditions
•
C-H Aroylation
•
decarboxylation • N-sulfoximine benzamides • Pd-catalysis
[1] a) C. J. Lim, S. H. Kim, B. H. Lee, K.-S. Oh, K. Y. Yi, Bioorg. Med. Chem.
Lett. 2012, 22, 427; b) A. F. Watson, J. Liu, K. Bennaceur, C. J. Drummond, J.
A. Endicott, B. T. Golding, R. J. Griffin, K. Haggerty, X. Lu, J. M. McDonnell, D.
R. Newell, M. E. M. Noble, C. H. Revill, C. Riedinger, Q. Xu, Y. Zhao, J. Lunec,
I. R. Hardcastle, Bioorg. Med. Chem. Lett. 2011, 21, 5916; c) P. Vineet, J. R.
Maria, G. Federico, Anti-Cancer Agents Med. Chem. 2008, 8, 638; d) D.
Chowdhury, S. Maurya, M. B. Pandey, V. B. Pandey, B. K. Sarma, U. P. Singh,
Mycobiology 2005, 33, 206; e) T. Ukita, Y. Nakamura, A. Kubo, Y. Yamamoto,
Y. Moritani, K. Saruta, T. Higashijima, J. Kotera, M. Takagi, K. Kikkawa, K.
Omori, J. Med. Chem. 2001, 44, 2204.
[13] J. Miao, H. Ge, Org. Lett. 2013, 15, 2930.
[14] J. K. Laha, K. V. Patel, S. Sharma, ACS Omega 2017, 2, 3806.
[15] K. Jing, J.-P. Yao, Z.-Y. Li, Q.-L. Li, H.-S. Lin, G.-W. Wang, J. Org. Chem.
2017, 82, 12715.
[16] T. C. Sparks, G. B. Watson, M. R. Loso, C. Geng, J. M. Babcock, J. D.
Thomas, Pestic. Biochem. Physiol. 2013, 107, 1.
[17] U. Lücking, Angew. Chem. Int. Ed. 2013, 52, 9399.
[18] a) C. Sambiagio, D. Schönbauer, R. Blieck, T. Dao-Huy, G. Pototschnig,
P. Schaaf, T. Wiesinger, M. F. Zia, J. Wencel-Delord, T. Besset, B. U. W.
Maes, M. Schnürch, Chem. Soc. Rev. 2018, 47, 6603; b) V. Bizet, C. M. M.
Hendriks, C. Bolm, Chem. Soc. Rev. 2015, 44, 3378.
[2] a) S. Singh, N. R. Prasad, E. E. Chufan, B. A. Patel, Y.-J. Wang, Z.-S.
Chen, S. V. Ambudkar, T. T. Talele, J. Med. Chem. 2014, 57, 4058; b) J. Lee,
S. J. Kim, H. Choi, Y. H. Kim, I. T. Lim, H.-m. Yang, C. S. Lee, H. R. Kang, S.
K. Ahn, S. K. Moon, D.-H. Kim, S. Lee, N. S. Choi, K. J. Lee, J. Med. Chem.
2010, 53, 6337; c) Y. Deng, Y.-W. Chin, H. Chai, W. J. Keller, A. D. Kinghorn,
J. Nat. Prod. 2007, 70, 2049; d) K. R. Romines, G. A. Freeman, L. T. Schaller,
J. R. Cowan, S. S. Gonzales, J. H. Tidwell, C. W. Andrews, D. K. Stammers, R.
J. Hazen, R. G. Ferris, S. A. Short, J. H. Chan, L. R. Boone, J. Med. Chem.
2006, 49, 727; e) S. Gobec, P. Brožič, T. L. Rižner, Bioorg. Med. Chem 2005,
15, 5170; f) D. F. Wyss, A. Arasappan, M. M. Senior, Y.-S. Wang, B. M. Beyer,
F. G. Njoroge, M. A. McCoy, J. Med. Chem. 2004, 47, 2486; g) D. M. Gapinski,
B. E. Mallett, L. L. Froelich, W. T. Jackson, J. Med. Chem. 1990, 33, 2798; h)
D. Evans, M. E. Cracknell, J. C. Saunders, C. E. Smith, W. R. N. Williamson,
W. Dawson, W. J. F. Sweatman, J. Med. Chem. 1987, 30, 1321; i) W. A.
Sexton, W. G. Templeman, Nature 1948, 161, 974.
[19] a) M. Tamizmani, B. Ramesh, M. Jeganmohan, J. Org. Chem. 2018, 83,
3746; b) K. Ghosh, M. Shankar, R. K. Rit, G. Dubey, P. V. Bharatam, A. K.
Sahoo, J. Org. Chem. 2018, 83, 9667; c) M. Shankar, T. Guntreddi, E.
Ramesh, A. K. Sahoo, Org. Lett. 2017, 19, 5665; d) K. Raghuvanshi, D. Zell, L.
Ackermann, Org. Lett. 2017, 19, 1278; e) K. Ghosh, R. K. Rit, E. Ramesh, A.
K. Sahoo, Angew. Chem. Int. Ed. 2016, 55, 7821; f) M. R. Yadav, M. Shankar,
E. Ramesh, K. Ghosh, A. K. Sahoo, Org. Lett. 2015, 17, 1886; g) Y. Cheng, C.
Bolm, Angew. Chem. Int. Ed. 2015, 54, 12349; h) R. K. Rit, M. R. Yadav, K.
Ghosh, M. Shankar, A. K. Sahoo, Org. Lett. 2014, 16, 5258; i) W. Dong, K.
Parthasarathy, Y. Cheng, F. Pan, C. Bolm, Chem. Eur. J. 2014, 20, 15732; j)
M. R. Yadav, R. K. Rit, A. K. Sahoo, Org. Lett. 2013, 15, 1638; k) L. Wang, D.
L. Priebbenow, L. H. Zou, C. Bolm, Adv. Synth. Catal. 2013, 355, 1490; l) W.
Dong, L. Wang, K. Parthasarathy, F. Pan, C. Bolm, Angew. Chem. Int. Ed.
This article is protected by copyright. All rights reserved.

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Chemistry - An Asian Journal
FULL PAPER
2013, 52, 11573; m) M. R. Yadav, R. K. Rit, A. K. Sahoo, Chem. Eur. J. 2012,
18, 5541.
[20] a) S. Paul, M. Bhakat, J. Guin, Chem. Asian. J. 2019, 14, 3154; b) P.
Biswas, J. Guin, J. Org. Chem. 2018, 83, 5629; c) P. Biswas, S. Paul, J. Guin,
Synlett 2017, 28, 1244; d) P. Biswas, S. Paul, J. Guin, Angew. Chem. Int. Ed.
2016, 55, 7756; e) S. Paul, J. Guin, Chem. Eur. J. 2015, 21, 17618.
[21] a) D. Saha, P. Das, P. Biswas, J. Guin, Chem. Asian. J. 2019, 14, 4534;
b) P. Das, J. Guin, ChemCatChem 2018, 10, 2370; c) P. Das, D. Saha, D.
Saha, J. Guin, ACS Catal. 2016, 6, 6050.
[22] E. M. Simmons, J. F. Hartwig, Angew. Chem. Int. Ed. 2012, 51, 3066.
[23] For binuclear PdIII-intermediate, see: a) M. C. Nielsen, E. Lyngvi, F.
Schoenebeck, J. Am. Chem. Soc. 2013, 135, 1978; b) D. C. Powers, T. Ritter,
Acc. Chem. Res. 2012, 45, 840; c) D. C. Powers, D. Benitez, E. Tkatchouk, W.
A. Goddard, T. Ritter, J. Am. Chem. Soc. 2010, 132, 14092; d) D. C. Powers,
T. Ritter, Nat. Chem. 2009, 1, 302; e) D. C. Powers, M. A. L. Geibel, J. E. M. N.
Klein, T. Ritter, J. Am. Chem. Soc. 2009, 131, 17050; f) N. R. Deprez, M. S.
Sanford, J. Am. Chem. Soc. 2009, 131, 11234; g) F. A. Cotton, I. O. Koshevoy,
P. Lahuerta, C. A. Murillo, M. Sanaú, M. A. Ubeda, Q. Zhao, J. Am. Chem.
Soc. 2006, 128, 13674; h) R. H. Crabtree, Science 2002, 295, 288; i) F. A.
Cotton, J. Gu, C. A. Murillo, D. J. Timmons, J. Am. Chem. Soc. 1998, 120,
13280; j) T. Yoneyama, R. H. Crabtree, J. Mol. Catal. A 1996, 108, 35.
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Prasenjit Das, Promita Biswas and Joyram
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Pd-catalyzed
decarboxylative
ortho
C(sp2)-H aroylation of N-sulfoximine
benzamides at room temperature
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