Rhodium(III)-Catalyzed C?H Alkynylation of N-Methylsulfoximines

Article abstract of DOI:10.1002/asia.201800889

A rhodium(III)-catalyzed direct C?H alkynylation of a wide range of N-methylsulfoximines with (bromoethynyl)triisopropylsilane has been developed. This protocol is compatible with both (S,S)-diaryl sulfoximines and (S,S)-alkyl aryl sulfoximines, and shows mild conditions, and good functional group tolerance. The synthetic utility of this method has been demonstrated by subsequent various transformations of the products.

Full text of DOI:10.1002/asia.201800889

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Rhodium(III)-Catalyzed C-H Alkynylation of N-Methylsulfoximines
Authors: Xi-Sheng Wang, Tao Wang, Yi-Ning Wang, and Rui Wang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.201800889
Link to VoR: http://dx.doi.org/10.1002/asia.201800889
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201800889
Chemistry - An Asian Journal
COMMUNICATION
Rhodium(III)-Catalyzed C-H Alkynylation of N-Methylsulfoximines
Tao Wang, Yi-Ning Wang, Rui Wang, and Xi-Sheng Wang*[a]
Abstract: A Rhodium(III)-catalyzed direct C-H alkynylation of a wide
range of N-methylsulfoximines with (bromoethynyl)triisopropylsilane
has been developed. This protocol is compatible with both S,S-diaryl
sulfoximines and S,S-alkyl aryl sulfoximines, and demonstrates mild
conditions, good functional group tolerance. The synthetic utility of
this method has been demonstrated by subsequent various
transformations of the products.
sulfoximines is still normal Sonogashira-type cross-coupling
from ortho-bromo or -iodo sulfoximines (Scheme 1a),[5m,9] where
the requirement of preinstalling halogen atoms onto the arenes
definitely caused some problems on atom- and step-economy
for the synthesis of target sulfoximines. Herein, we reported a
rhodium(III)-catalyzed direct alkynylation of ortho-C-H bonds on
aryl sulfoximines, in which both diaryl and S,S-alkyl aryl
sulfoximines are well compatible with this transformation
(Scheme 1b). This air- and moisture-tolerant reaction is easy-to-
handle and proceeds under mild conditions.
As an interesting and important class of scaffolds in organic
molecules, sulfoximines not only exist widely in diverse natural
products, pharmaceuticals and agrochemicals,[1] but also are
utilized as chiral auxiliaries and ligands in organic synthesis.[2]
Therefore, the development of novel synthetic approaches to
construct new sulfoximines has long received intensive
attentions.[2c,2g,3] In the past several decades, transition-metal-
catalyzed direct functionalization of C-H bonds has emerged as
an strategy for total synthesis of complex molecules and
intermediates,[4] which clearly demonstrates that the direct C-H
functionalization stands out as the most straightforward strategy
to synthesize functionalized sulfoximine. After the pioneering
work on rhodium-catalyzed oxidative annulation of sulfoximines
and alkynes from Bolm and coworkers,[5a] several groups have
expanded the coupling partners of sulfoximines to diazo
compounds,[5b] olefins,[5c-g] pyridotriazoles,[5h] 3-diazoindolin-2-
imines,[5i] -MsO/TsO ketones,[5j] sulfoxonium ylides,[5k] etc.[5l,5m]
Furthermore, inspired by the well established Rh(III) catalytic
system, several other transition-metals, including Ru(II),[5n]
Cp*Co(III),[5o] and Cp*Ir(III),[5p] have been successfully applied to
direct C-H functionalization of sulfoximines. However, to the best
of our knowledge, direct alkynylation of C-H bonds of
sulfoximines has never been reported and remains as a
challenge.
Scheme 1. Synthesis of ortho-alkynylated sulfoximines.
Our initial investigation commenced with N-methylsulfoximine
1c as the pilot substrate and TIPS-protected bromoacetylene 2
as the coupling partner in the presence of catalytic amount of
Cp*Rh(CH3CN)3(SbF6)2 (7 mol%) at 90 °C for 12 h. To our
delight, the desired alkynylated sulfoximines 3c was obtained
successfully in 86% yield when Ag2CO3 (0.8 equiv) was used as
oxidant and MeOH as solvent (Table 1, entry 1). Interestingly, a
careful screening of solvents indicated that 1,4-dioxane, toluene,
THF and 1,2-DCE gave almost the same yields as MeOH, while
only CH3CN and DMF afforded 3c in low yields (entries 2-7). To
further improve the yield, we next examined silver salts (entries
8-12) and rhodium catalysts (See Table S3, SI) using 1,2-DCE
Alkynes are versatile building blocks in synthetic chemistry
and exist widely in natural products, drugs and organic
materials,[6] thus the selective incorporation of alkyne groups into
organic molecules is of great significance. For example, the
palladium/copper co-catalyzed cross-coupling between aryl
halides and terminal alkynes, known as Sonogashira coupling
reaction, has long been realized as a common and valuable tool
for the construction of C(sp2)−C(sp) bonds.[7] Along with the
rapid expansion of transition-metal-catalyzed C-H activation in
recent decades, direct C-H alkynylation reactions have recently
been developed as a desirable method for facile synthesis of
alkyne derivatives from C(sp2)-H and C(sp3)-H bonds.[8] But till
now, the only known method to make ortho-alkynylated
as
solvent,
which
revealed
that
Ag2CO3
and
Cp*Rh(CH3CN)3(SbF6)2 were the best choices. Furthermore, the
decrease of the amount of sulfoximine 1c to 1.2 equiv could
result in a somewhat lower yield (81%, entry 13). Notably,
almost the same yield was afforded when the Rh(III) catalyst
loading was decreased to 5 mol% (entry 14). Finally, control
experiments indicated that only trace amount of 3c was obtained
without adding Ag2CO3 (entry 15), and no desired product was
detected in the absence of the rhodium catalyst (entry 16).
[a]
T. Wang, Y.-N. Wang, R. Wang, and Prof. Dr. X.-S. Wang
Hefei National Laboratory for Physical Sciences at the Microscale
and Department of Chemistry
With the optimal reaction conditions in hand, we next sought
to evaluate the scope and generality of the N-methylsulfoximines
in this protocol. As shown in Scheme 2, a variety of symmetrical
and unsymmetrical diphenyl sulfoximines with different
substituents, including both electron-donating groups, such as
University of Science and Technology of China
Hefei, Anhui 230026, China
E-mail: xswang77@ustc.edu.cn
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800889
Chemistry - An Asian Journal
COMMUNICATION
Table 1. Optimization of the reaction conditions.[a]
expected, direct alkynylation of ortho-substitued sulfoximines
exhibited lower reactivity, probably due to the steric hindrance of
ortho-substituents (1d, 1o, 1q). It is noteworthy that C-H
alkynylation occurred mainly at ortho-Me-substituted aromatic
ring instead of phenyl group in the case of unsymmetrical diaryl
sulfoximine 1q. Presumably, the unexpected consequence could
be explained by an unfavorable steric interaction between the
Entry
1
Solvent
MeOH
CH3CN
dioxane
toluene
THF
AgX
Yield(%)[b]
Me-containing
aryl
ring
and
the
bulky
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
AgNO3
AgOTf
86
12
pentamethylcyclopentadienyl (Cp*) ligand on rhodium during the
process of C-H cleavage.[10]
To our satisfaction, this protocol displayed good tolerance
toward S-alkyl S-aryl sulfoximine as well, albeit in a slightly lower
2
3
87
4
88
Scheme 2. Scope of sulfoximines.[a]
5
88
6
DMF
27
7
DCE
88
8
DCE
8
9
DCE
72
10
11
12
13[c]
14[d]
15
16[e]
DCE
Ag2O
85
DCE
AgOAc
AgOTFA
Ag2CO3
Ag2CO3
none
67
DCE
trace
81
DCE
DCE
87(84)
5
DCE
DCE
Ag2CO3
0
[a] Unless otherwise noted, reactions were carried out with 1c (0.225 mmol,
1.5 equiv), 2 (0.15 mmol, 1.0 equiv), Cp*Rh(CH3CN)3(SbF6)2 (7 mol%), AgX
(1.6 equiv) in 1.0 mL solvent at 90 ˚C for 12 h. [b] The yield was determined by
1H NMR analysis of the crude reaction mixture using CH2Br2 as the internal
standard. Isolated yield is shown in parentheses. [c] 1c (0.18 mmol). [d]
Cp*Rh(CH3CN)3(SbF6)2 (5 mol%). [e] No Cp*Rh(CH3CN)3(SbF6)2.
methyl (1c), methoxy (1e), phenyl (1f), and electron-withdrawing
groups, such as bromo (1k), trifluoromethyl (1l), nitro (1m) and
ester
(1n),
were
smoothly
alkynylated
with
(bromoethynyl)triisopropylsilane. Moreover, the tolerance of
halogens in this new method enabled the facile synthesis of
multi-substituted sulfoximines by transition-metal-catalyzed
cross-coupling reactions. Not surprisingly, diphenyl sulfoximine
(1a) and para-substituted sulfoximines bearing methyl (1b),
fluoro (1h), chloro (1i), bromo (1j) could afford the desired
products in good total yields (65% to 82%), albeit as mixtures of
mono- and dialkynylated sulfoximines with ratios ranging from
3.6:1 to 5.0:1. Notably, the alkynylation occurred at the less
hindered C-H bonds on the phenyl rings for almost all meta-
substituted sulfoximines with excellent regioselectivity, and the
coupling products could be obtained with even better yields (61%
to 89%). It should be noted that meta-fluoro substituted
substrate furnished three separable alkynylated products (3g,
o:o‘:di = 1:2.8:1.5), because of the little steric hindrance of
fluorine atom for C-H activation. β-Naphthyl-substituted
sulfoximine (1p) was also compatible with this reaction,
providing 3p in good yield with excellent selectivity. As we
[a] Unless otherwise noted, the reaction conditions were as follow: 1 (0.225
mmol, 1.5 equiv), 2 (0.15 mmol, 1.0 equiv), Cp*Rh(CH3CN)3(SbF6)2 (5 mol%)
and Ag2CO3 (0.8 equiv) in 1,2-DCE (1.0 mL) at 90 ˚C for 12 h; isolated yields
were reported. [b] Cp*Rh(CH3CN)3(SbF6)2 (7 mol%), 1 (0.3 mmol, 2.0 equiv).
[c] Cp*Rh(CH3CN)3(SbF6)2 (7 mol%),
1 (0.45 mmol, 3.0 equiv). [d]
Cp*Rh(CH3CN)3(SbF6)2 (10 mol%), 1 (0.45 mmol, 3.0 equiv).
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800889
Chemistry - An Asian Journal
COMMUNICATION
but still acceptable yield. Similarly, C-H bonds located in the less
hindered position of meta-substituted sulfoximines could be
selectively alkynylated with comparatively higher yields. A
variety of functional groups, such as methyl (1t), methoxy (1u),
chloro (1w) and bromo (1x), were also compatible with this
transformation. Particularly, S-2-naphthyl S-methyl sulfoximine
1y showed excellent site-selectivity in this reaction, furnishing 3y
in 83% yield. Meanwhile, para-substituted sulfoximines (1s, 1v)
and 1r gave only moderate yields in this catalytic system.
Additionally,
S-ethyl-
and
isopropyl-substituted
S-aryl
sulfoximines (1z and 1aa) were also proved to be suitable
substrates, which could be alkynylated in 80% and 45% yield,
respectively.
To demonstrate the synthetic utility of this new methodology,
further derivatizations of the ortho-alkynylated sulfoximines were
next carried out. As shown in Scheme 3, palladium-catalyzed
Suzuki coupling reaction and Buchwald-Hartwig reaction were
applied with meta-Bromo-substituted product 3x to get multi-
functionalized sulfoximines. Both phenyl and morpholine group
were incorporated into ortho-alkynylated sulfoximines with
excellent yields (4, 5). More interestingly, TBAF-mediated
cleavage of the TIPS group of 3y proceeded smoothly to give
terminal alkyne 6, which could definitely be used for further
elaboration in organic synthesis.
Scheme 4. Proposed reaction mechanism.
Experimental Section
General Procedure for Rhodium-Catalyzed C-H Alkynylation of N-
Methylsulfoximines:
To an oven-dried 35 mL screw-cap sealed tube equipped with a
magnetic stir bar was added Cp*Rh(CH3CN)3(SbF6)2 (5-10 mol%,
0.0075-0.015 mmol, 6.2-12.4 mg), Ag2CO3 (0.8 equiv, 0.12 mmol, 33.1
mg), substrate 1 (1.5-3.0 equiv, 0.225-0.45 mmol), TIPS-protected
bromoacetylene
2 (1.0 equiv, 0.15 mmol, 39.2 mg) and 1,2-
dichloroethane (1.0 mL) under air atmosphere. The vessel was then
sealed with a Teflon screw-cap and placed into a preheated oil bath at
90 °C for 12 h. After completion, the reaction mixture was cooled to room
temperature and was directly filtered through a short pad of silica gel,
washed with EtOAc. The filtrate was concentrated under vacuum and
purified by chromatography on silica gel to obtain the corresponding
product 3.
Scheme 3. Derivatizations of ortho-alkynylated sulfoximines.
On the basis of previous reports,[11] a plausible mechanism Acknowledgements
was proposed as below (Scheme 4). The catalytic cycle is
initiated by coordination of Rh(III) species to sulfoximines and
subsequent C-H activation with assistance of ligated base
generates a five-membered rhodacycle intermediate I. The
intermediate undergoes ligand exchange to coordinate with
bromoacetylene 2, followed by alkyne insertion and Ag2CO3-
assisted bromide elimination delivers the final products 3 and
regenerates rhodium(III) catalyst.
We gratefully acknowledge the National Basic Research
Program of China (973 Program 2015CB856600), the National
Science Foundation of China (21522208, 21772187, 21602213)
for financial support.
Keywords: Rhodium(III) • C-H activation • Alkynylation •
Sulfoximine • Bromoacetylene
In conclusion, we have developed a Cp*Rh(III)-catalyzed
direct C-H alkynylation of N-methylsulfoximines. Both S,S-diaryl
and S,S-alkyl aryl sulfoximines are compatible with the
transformation, and a broad range of functional groups are well
tolerated in this method under mild conditions. The synthetic
utility of this protocol has been demonstrated by subsequent
various derivatizations of the alkynylated products.
[1]
a) M. Kahraman, S. Sinishtay, P. M. Dolan, T. W. Kensler, S. Peleg, U.
Saha, S. S. Chuang, G. Bernstein, B. Korczak, G. H. Posner, J. Med.
Chem. 2004, 47, 6854-6863; b) T. C. Sparks, G. B. Watson, M. R. Loso,
C. Geng, J. M. Babcock, J. D. Thomas, Pestic. Biochem. Physiol. 2013,
107, 1-7; c) M. Frings, C. Bolm, A. Blum, C. Gnamm, Eur. J. Med.
Chem. 2017, 126, 225-245; d) V. L. R. Jeannoda, J. Valisolalao, E. E.
Creppy, G. Dirheimer, Phytochemistry 1985, 24, 854-855; e) R. Dillard,
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800889
Chemistry - An Asian Journal
COMMUNICATION
T. Yen, P. Stark, D. Pavey, J. Med. Chem. 1980, 23, 717-722; f) V. L. R.
Jeannoda, D. A. D. Rakoto-Ranoromalala, J. Valisolalao, E. E. Creppy,
G. Dirheimer, J. Ethnopharmacol. 1985, 14, 11-17; g) Y. Zhu, M. R.
Loso, G. B. Watson, T. C. Sparks, R. B. Rogers, J. X. Huang, B. C.
Gerwick, J. M. Babcock, D. Kelley, V. B. Hegde, B. M. Nugent, J. M.
Renga, I. Denholm, K. Gorman, G. J. DeBoer, J. Hasler, T. Meade, J. D.
Thomas, J. Agric. Food Chem. 2011, 59, 2950-2957; h) H. Yu, Z. Qin,
H. Dai, X. Zhang, X. Qin, T. Wang, J. Fang, J. Agric. Food Chem. 2008,
56, 11356-11360; i) U. Lꢀcking, Angew. Chem. 2013, 125, 9570-9580;
Angew. Chem. Int. Ed. 2013, 52, 9399-9408.
Angew. Chem. Int. Ed. 2015, 54, 12349-12352; c) K. Parthasarathy, C.
Bolm, Chem.
- Eur. J. 2014, 20, 4896-4900; d) W. Dong, K.
Parthasarathy, Y. Cheng, F. Pan, C. Bolm, Chem. - Eur. J. 2014, 20,
15732-15736; e) J. Wen, D. P. Tiwari, C. Bolm, Org. Lett. 2017, 19,
1706-1709; f) J. Wen, H. Cheng, G. Raabe, C. Bolm, Org. Lett. 2017,
19, 6020-6023; g) Y. Li, L. Dong, Org. Biomol. Chem. 2017,15, 9983-
9986; h) W. H. Jeon, J.-Y. Son, J. E. Kim, P. H. Lee, Org. Lett. 2016, 18,
3498-3501; i) G. H. Ko, J.-Y. Son, H. Kim, C. Maeng, Y. Baek, B. Seo,
K. Um, P. H. Lee, Adv. Synth. Catal. 2014, 356, 1461-1479; j) R. K.
Chinnagolla, A. Vijeta, M. Jeganmohan, Chem. Commun. 2015, 51,
12992-12995; k) G. Zheng, M. Tian, Y. Xu, X. Chen, X. Li, Org. Chem.
Front. 2018, 5, 998-1002; l) Y. Cheng, W. Dong, H. Wang, C. Bolm,
Chem. - Eur. J. 2016, 22, 10821-10824; m) Y. Cheng, W. Dong, K.
Parthasarathy, C. Bolm, Org. Lett. 2017, 19, 726-729; n) J. Huang, Y.
Huang, T. Wang, Q. Huang, Z. Wang, Z. Chen, Org. Lett. 2017, 19,
1128-1131; o) J. Huang, Y. Huang, T. Wang, Q. Huang, Z. Wang, Z.
Chen, Org. Lett. 2017, 19, 1128-1131; p) Y. N. Aher, D. M. Lade, A. B.
Pawar, Chem. Commun. 2018, 54, 6288-6291.
[2]
a) H. Okamura, C. Bolm, Chem. Lett. 2004, 33, 482-487; b) M.
Reggelin, C. Zur, Synthesis 2000, 1-64; c) X. Shen, J. Hu, Eur. J. Org.
Chem. 2014, 2014, 4437-4451; d) C. Worch, A. C. Mayer, C. Bolm in
Organosulfur Chemistry in Asymmetric Synthesis (Eds.: T. Toru, C.
Bolm), Wiley-VCH, Weinheim, 2008; p 209 and references therein; e) C.
R. Johnson, Acc. Chem. Res. 1973, 6, 341-347; f) C. Bolm, D.
Kaufmann, M. Zehnfer, M. Neuburger, Tetrahedron Lett. 1996, 37,
3985-3988; g) V. Bizet, R. Kowalczyk, C. Bolm, Chem. Soc. Rev. 2014,
43, 2426-2438; h) H.-J. Gais, Heteroat. Chem. 2007, 18, 472-481; i) C.
Bolm, O. Simić, J. Am. Chem. Soc. 2001, 123, 3830-3831.
[6]
a) F. Diederich, P. J. Stang, R. R. Tykwinski, Acetylene Chemistry:
Chemistry, Biology and Material Science; Wiley-VCH: Weinheim,
Germany, 2005; b) S. Diez-González, Catal. Sci. Technol. 2011, 1,
166-178; c) J. P. Brand, J. Waser, Chem. Soc. Rev. 2012, 41, 4165-
4179; d) I. V. Alabugin, B. Gold, J. Org. Chem. 2013, 78, 7777-7784; e)
I. A. Meretina, B. I. Ionin, J. C. Tebby, Alkynes in Cycloadditions; Wiley-
Blackwell: New Jersey, USA, 2013.
[3]
For selected examples of preparation of sulfoximines: a) V. Bizet, C. M.
M. Hendriks, C. Bolm, Chem. Soc. Rev. 2015, 44, 3378-3390; b) L.
Wang, H. Huang, D. Priebbenow, F. Pan, C. Bolm, Angew. Chem. 2013,
125, 3562-3564; Angew. Chem. Int. Ed. 2013, 52, 3478-3480; c) R.
Pirwerdjan, D. Priebbenow, P. Becker, P. Lamers, C. Bolm, Org. Lett.
2013, 15, 5397-5399; d) A. Tota, M. Zenzola, S. J. Chawner, S. S.
John-Campbell, C. Carlucci, G. Romanazzi, L. Degennaro, J. A. Bull, R.
Luisi, Chem. Commun. 2017, 53, 348-351; e) M. Zenzola, R. Doran, L.
Degennaro, R. Luisi, J. A. Bull, Angew. Chem. 2016, 128, 7319-7323;
Angew. Chem. Int. Ed. 2016, 55, 7203-7207; f) D. Priebbenow, P.
Becker, C. Bolm, Org. Lett. 2013, 15, 6155-6157; g) X. Chen, L. Wang,
M. Frings, C. Bolm, Org. Lett. 2014, 16, 3796-3799. h) J. Wang, M.
Frings, C. Bolm, Chem. - Eur. J. 2014, 20, 966-969; i) J. Miao, N.
Richards, H. Ge, Chem. Commun. 2014, 50, 9687-9689; j) F. Teng, J.
Cheng, C. Bolm, Org. Lett. 2015, 17, 3166-3169; k) Y. Zou, J. Xiao, Z.
Peng, W. Dong, D. An, Chem. Commun. 2015, 51, 14889-14892; l) Z.
Chen, J. Huang, Z. Wang, J. Org. Chem. 2016, 81, 9308-9314; m) R.
Pirwerdjan, P. Becker, C. Bolm, Org. Lett. 2016, 18, 3307-3309.
[7]
[8]
a) E. Negishi, L. Anastasia, Chem. Rev. 2003, 103, 1979-2018; b) H.
Doucet, J.-C. Hierso, Angew. Chem. 2007, 119, 850-888; Angew.
Chem. Int. Ed. 2007, 46, 834-871; c) R. Chinchilla, C. Nájera. Chem.
Soc. Rev. 2011, 40, 5084-5121; d) R. Chinchilla, C. Nájera, Chem. Rev.
2014, 114, 1783-1826; e) D. Wang, S. Gao, Org. Chem. Front. 2014, 1,
556-566.
For selected examples of C-H alkynylation: a) D. A. Colby, R. G.
Bergman, J. A. Ellman, Chem. Rev. 2010, 110, 624-655; b) A. S.
Dudnik, V. Gevorgyan, Angew. Chem. 2010, 122, 2140-2142; Angew.
Chem. Int. Ed. 2010, 49, 2096-2098; c) Z. Chen, B. Wang, J. Zhang, W.
Yu, Z. Liu, Y. Zhang, Org. Chem. Front. 2015, 2, 1107-1295; d) S. H.
Kim, J. Yoon, S. Chang, Org. Lett. 2011, 13, 1474-1477; e) C. Feng, D.
Feng, Y. Luo, T.-P. Loh, Org. Lett. 2014, 16, 5956-5959; f) C. Feng, T.-
P. Loh, Angew. Chem. 2014, 126, 2760-2764; Angew. Chem. Int. Ed.
2014, 53, 2722-2726; g) C. Feng, D. Feng, T.-P. Loh, Chem. Commun.
2014, 50, 9865-9868; h) X. Zhang, Z. Qi, J. Gao, X. Li, Org. Biomol.
Chem. 2014, 12, 9329-9332; i) Z.-Z. Zhang, B. Liu, C.-Y. Wang, B.-F.
Shi, Org. Lett. 2015, 17, 4094-4097; j) N. Sauermann, M. J. Gonzalez,
L. Ackermann, Org. Lett. 2015,17, 5316-531; k) X. Ye, C. Xu, L. Wojtas,
N. G. Akhmedov, H. Chen, X. Shi, Org. Lett. 2016, 18, 2970-2973; l) V.
G. Landge, M. K. Sahoo, S. P. Midya, G. Jaiswal, E. Balaraman, Dalton
Trans. 2015, 44, 15382-15386; m) Y. Ano, M. Tobisu, N. Chatani, H. Fu,
P.-X. Shen, J. He, F. Zhang, S. Li, P. Wang, T. Liu, J.-Q. Yu, Angew.
Chem. 2017, 129,1899-1902; Angew. Chem. Int. Ed. 2017, 56, 1873-
1876.
[4]
For selected examples of transition-metal-catalyzed C-H functionaliz-
ation: a) X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem.
2009, 121, 5196-5217; Angew. Chem. Int. Ed. 2009, 48, 5094-5115; b)
K. M. Engle, T.-S. Mei, M. Wasa, J.-Q. Yu, Acc. Chem. Res. 2012, 45,
788-802; c) G. Song, F. Wang, X. Li, Chem. Soc. Rev., 2012, 41, 3651-
3678; d) D. A. Colby, A. S. Tsai, R. G. Bergman, J. A. Ellman, Acc.
Chem. Res. 2012, 45, 814-825; e) T. Satoh, M. Miura, Chem. - Eur. J.
2010, 16, 11212-11222; f) D. A. Colby, R. G. Bergman, J. A. Ellman,
Chem. Rev. 2010, 110, 624-655; g) M. Jeganmohan, R. Manikandan,
Chem. Commun. 2017, 53, 8931-8947; h) S. Ruiz, P. Villuendas, E. P.
Urriolabeitia, Tetrahedron Lett. 2016, 57, 3413-3432; i) S. D. Sarkar, W.
Liu, S. I. Kozhushkov, L. Ackermann, Adv. Synth. Catal. 2014, 356,
1461-1479; j) P. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem. Rev.
2012, 112, 5879-5918; k) L. C. M. Castro, N. Chatani, Chem. Lett. 2015,
44, 410-421; l) M. Bera, S. Agasti, R. Chowdhury, R. Mondal, D. Pal, D.
Maiti, Angew. Chem. 2017, 129, 5356-5360; Angew. Chem. Int. Ed.
2017, 56, 5272-5276; m) A. Deb, S. Bag, R. Kancherla, D. Maiti, J. Am.
Chem. Soc. 2014, 136, 13602-13605.
[9]
M. Harmata, K. Rayanil, M. G. Gomes, P. Zheng, N. L. Calkins, S.-Y.
Kim, Y. Fan, V. Bumbu, D. R. Lee, S. Wacharasindhu, X. Hong, Org.
Lett. 2005, 7, 143-145.
[10] D. R. Stuart, P. Alsabeh, M. Kuhn, K. Fagnou, J. Am. Chem. Soc. 2010,
132, 18326-18339.
[11]
E. Tan, O. Quinonero, M. E. de Orbe, A. M. Echavarren, ACS Catal.
2018, 8, 2166−2172.
[5] a) W. Dong, L. Wang, K. Parthasarathy, F. Pan, C. Bolm, Angew. Chem.
2013, 125, 11787-11790; Angew. Chem. Int. Ed. 2013, 52, 11573-
11576; b) Y. Cheng, C. Bolm, Angew. Chem. 2015, 127, 12526-12529;
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201800889
Chemistry - An Asian Journal
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
COMMUNICATION
Tao Wang, Yi-Ning Wang, Rui Wang,
and Xi-Sheng Wang*
Page No. – Page No.
Rhodium(III)-Catalyzed C-H
Alkynylation of N-Methylsulfoximines
A
Rhodium(III)-catalyzed direct C-H alkynylation of a wide range of N-
methylsulfoximines with (bromoethynyl)triisopropylsilane has been developed. This
protocol is compatible with both S,S-diaryl sulfoximines and S,S-alkyl aryl
sulfoximines, and demonstrates mild conditions, good functional group tolerance.
The synthetic utility of this method has been demonstrated by subsequent various
transformations of the products.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.