Nickel-Catalyzed Sulfonylation of C(sp2)–H Bonds with Sodium Sulfinates

Article abstract of DOI:10.1002/adsc.201700290

The first nickel-catalyzed ortho-sulfonylation of C(sp²)–H bonds with sodium sulfinates directed by (pyridin-2-yl)isopropylamine (PIP-amine) is described. This strategy exhibits a broad substrate scope and good functional group tolerance with high monosulfonylation selectivity. Besides arenes and heteroarenes, the reaction can also be extended to alkenes, providing diverse diaryl and alkyl aryl sulfones in high yields. Furthermore, a plausible Ni(I)/Ni(III) mechanism is outlined based on our experimental results and related precedents. (Figure presented.).

Full text of DOI:10.1002/adsc.201700290

Title: Nickel-Catalyzed Sulfonylation of C(sp2)–H Bonds with Sodium
Sulfinates
Authors: Shuang-Liang Liu, Xue-Hong Li, Shu-Sheng Zhang, Sheng-
Kai Hou, Guang-Chao Yang, and Jun-Fang Gong
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700290
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10.1002/adsc.201700290
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Nickel-Catalyzed Sulfonylation of C(sp2)–H Bonds with Sodium
Sulfinates
Shuang-Liang Liu,a Xue-Hong Li,a Shu-Sheng Zhang,a Sheng-Kai Hou,a Guang-Chao
Yang,a Jun-Fang Gong,a,* and Mao-Ping Song a,*
a
College of Chemistry and Molecular Engineering, Henan Key laboratory of Chemical Biology and Organic Chemistry,
Zhengzhou University, Zhengzhou 450001, P. R. China
E-mail: mpsong@zzu.edu.cn or gongjf@zzu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
assisted C-H functionalizations has emerged as a
Abstract. The first Ni-catalyzed ortho-sulfonylation of
C(sp2)–H bonds with sodium sulfinates directed by (pyridin- hotspot in chemical research.[7b-f]
2-yl)isopropylamine (PIP-amine) is described. This strategy
exhibits a broad substrate scope and good functional group
tolerance with high monosulfonylation selectivity. Besides
arenes and heteroarenes, the reaction can also be extended to
alkenes, providing diverse diaryl and alkyl-aryl sulfones in
In 2009, Dong and coworkers reported the first
example of direct C(sp2)-H bond sulfonylation with
arylsulfonyl chlorides promoted by pyridine under Pd
catalysis.[8] Since then, extensive efforts have been
devoted to the selective sulfonylation of C–H bonds
with sulfonyl chlorides or sulfinate salts catalyzed or
mediated by various transition metals including Pd,[8,9]
Rh,[10] Cu[11] and Ru.[12] Despite the impressive
progress, particularly the use of inexpensive Cu salt as
the catalyst,[11a,b,d,f-j] C-H sulfonylation catalyzed or
mediated by the same inexpensive nickel remains
much less explored. To the best of our knowledge,
there are only two reports on this subject up to now.[13]
Furthermore, the achieved results were quite
unsatisfying with regard to the substrate scope,
selectivity, and reaction efficiency. As for the two
reports, one is disclosed by Chatani in 2015 which
concerned Ni-catalyzed ortho-sulfonylation of C–H
bonds in aromatic amides with arylsulfonyl chlorides
employing 5-chloro-8-aminoquinoline as the directing
group (Scheme 1a).[13a] The utilization of 5-chloro-8-
high yields. Furthermore,
a
plausible Ni(I)/Ni(III)
mechanism is outlined based on our experimental results and
related precedents.
Keywords: sulfonylation; C–H activation; nickel; sodium
sulfinates; (pyridin-2-yl)isopropylamine (PIP-amine)
The sulfone moiety is one of the common structural
units in organic molecules and widely found in
pharmaceutical compounds and functional materials.[1]
Sulfones also play important roles in synthetic
chemistry such as in the classical Ramberg–Backlund
reaction[2] and Julia olefination.[3] Consequently, the
synthesis of sulfones has been extensively explored.[4]
Traditional approaches mainly include oxidation of
sulfides or sulfoxides, sulfonylation of arenes in the
presence of strong acids, addition of sulfonyl radical
precursors to alkenes and alkynes, or cross-coupling
reaction of sulfinates with prefunctionalized coupling
partners such as halides, triflates, aryl boronic acids,
and diaryliodonium salts.[4a] However, these methods
aminoquinoline
instead
of
8-aminoquinoline
successfully avoided the formation of the C-5
sulfonylated quinolines. However, the narrow
substrate scope and low reactivity (11 examples, 21-
46% yields except the -naphthalyl substrate), the
formation of sulfides byproducts (up to 10%) due to
the use of PPh3 in the catalytic system as well as high
o
generally
face
problems
of
multi-step
reaction temperature (160 C) limited the application
prefunctionalization, poor regioselectivity and
functional group compatibility.
of this method. The other is reported by Kambe and
coworkers almost simultaneously which described a
similar sulfonylation in the presence of 50 mol% of Ni
In recent years, transition metal catalyzed C-H
activation has emerged as a simple and efficient tool
in organic synthesis.[5] During which, nickel has
exhibited its priority in terms of abundance, low-cost
and good catalytic performance.[6,7] Especially, since
the first report of Ni-catalyzed 2-pyridinylmethyl-
amine-assisted transformation of ortho C-H bonds by
Chatani and coworkers,[7a] this type of chelation
o
with the assistance of 8-aminoquinoline at 140 C
(Scheme 1b).[13b] Unfortunately, this methodology also
gave unsatisfying results: the desired ortho-
sulfonylated products were obtained in only 33-61%
yields (14 examples), always along with the ortho- and
C-5 disulfonylated byproducts (<2%). Therefore, the
development of highly regioselective and efficient
nickel protocols would still be highly desirable. To this
1
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10.1002/adsc.201700290
Advanced Synthesis & Catalysis
end and also as a continuation of our interest in cheap
metal-catalyzed bidentate directing group-assisted C-
H functionalization reactions,[14] herein we disclose
the first nickel-catalyzed ortho-sulfonylation of
C(sp2)–H bonds with the non-toxic and stable sodium
sulfinates accelerated by the 2-(pyridine-2-
yl)isopropylamine (PIP-amine) (Scheme 1c). The PIP-
amine has been developed by Shi and demonstrated as
a powerful directing group for diverse C-H
functionalizations.[15] Compared with the above two
methods based on Ni catalyst,[13] it is noteworthy that
our method exhibits good functional group tolerance
and high regioselectivity, providing a milder approach
to diverse diaryl and alkyl-aryl sulfones in modest to
excellent yields (33 examples, up to 90% yields).
Table 1. Optimization of the Reaction Conditions[a]
Entry
1
2
Solvent
DCE
DCE
Yield (%)
35[b]
73
3
4
5
MTBE
DME
THF
28
trace
24
6
7
8
toluene
CH3CN
1,4-dioxane
CHCl3
n-BuOH
DMAc
DMSO
DMF
trace
24
12
80
0
trace
0
0
9[c]
10
11
12
13
[a] Reaction conditions: 1a (0.2 mmol), PhSO2Na (0.4 mmol),
NiBr2 (10 mol%), PhCOOH (20 mol%) and Ag2CO3
(0.4 mmol) in solvent (1.0 mL) at 120 oC for 12 h under
air. Isolated yields.
[b]
Without PhCOOH.
With 8% disulfonylated product 2a'.
[c]
13) revealed that CHCl3 provided 2a in a maximum
yield of 80%, along with 8% of the disulfonylated
product 2a' (entry 9).
With the optimized conditions in hand, we
proceeded to investigate the scope of amides (Table 2).
Generally, both electron-rich (R = Me, OMe and t-Bu)
and electron-poor (R = CF3, COOMe and SO2Me)
substituents in the para-position of benzamides were
well tolerated, giving the corresponding products 2b-g
in moderate to high yields (55-85%). Reactions of
benzamides bearing halides including fluoride,
chloride, bromide and iodide on the para-position of
the benzene ring with PhSO2Na went quite well (2h-k,
75-87%), thus making further functionalization
possible. When meta-substituted benzamides were
reacted with PhSO2Na, sulfonylation occurred at the
less sterically hindered position, affording the
monosulfonylated products 2l-n exclusively (34-76%).
In the case of ortho-substituted substrates including a
1-naphth-amide, the desired products were obtained in
33-70% yields (2o-q). Interestingly, piperonylic acid
amide participated in this transformation with much
high efficiency, producing the 2-sulfonylated
benzamide 2r as the sole product (90%). This was
presumably due to the potential coordination property
of the dioxole, which may stabilize the arylnickel
interme- diates during the catalytic process.
Heteroaromatic amides such as thiophene and indole
derivatives were also feasible, albeit with lower yields
(2s-u, 21-34%). To our delight, the amide scope could
be extended to alkene substrates to produce the alkyl-
aryl sulfones, although higher temperature and catalyst
loading
Scheme 1. Ni-Catalyzed/Mediated Direct Sulfonylation of
C(sp2)−H Bonds.
We commenced our investigation by choosing the
reaction of benzamide derivative 1a with PhSO2Na as
a model. First, nickel catalysts were extensively
screened (see Table S1 in the Supporting Information
for details). It was found that NiBr2 could afford a
better yield and the desired monosulfonylated product
2a was obtained in 35% yield under 10 mol% of NiBr2
and 2.0 equiv of Ag2CO3 in 1,2-dichloroethane (DCE)
o
at 120 C for 12 h under air (Table 1, entry 1). The
effect of oxidants was then examined (Table S2 in the
Supporting Information). Notably, the use of Ag2CO3
as an oxidant was crucial for this transformation:
without oxidant or other oxidants such as AgOAc,
AgTFA, Ag2O, O2, PhI(OAc)2, K2S2O8, BQ,
.
Mn(OAc)3 2H2O, and NMO, led to obviously low
reactivity. To our delight, the addition of 20 mol%
PhCOOH significantly improved the yield to 73%
(entry 2). Encouraged by this, various carboxylate
ligands were tested but unfortunately, no improvement
was observed. Other ligands, such as BINOL, BINAP,
(BnO)2POOH, Xphos, PCy3, and 2,2'-dipyridyl, were
less effective or totally ineffective (Table S3 in the
Supporting Information). Finally,
screening of solvents (entries 3-
a
thorough
2
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10.1002/adsc.201700290
Advanced Synthesis & Catalysis
Table 2. Scope of Amides[a]
[a] Reaction conditions: 1 (0.2 mmol), PhSO2Na (0.4 mmol), NiBr2 (10 mol%), PhCOOH (20 mol%) and Ag2CO3 (0.4 mmol)
in CHCl3 (1.0 mL) at 120 oC for 12 h under air. Isolated yields.
To these examples, disulfonylated products were trace or not detected.
NiBr2 (20 mol%), PhCOOH (40 mol%).
[b]
[c]
[d]
NiBr2 (30 mol%), PhCOOH (60 mol%).
140 oC.
[e]
were required to achieve satisfactory conversion rates
(2v-x, 41-61%).
smoothly with 1a to afford the corresponding 2-
arylsulfonyl benzamides in moderate to good yields
(3a-g, 50-82%). Halides (F, Cl and Br) were well
The results for sulfonylation of benzamide 1a with
various sodium sulfinates were summarized in Table 3. tolerated in the reactions (3d-g), which could be used
It was found that arylsulfinates bearing both electron-
donating and -withdrawing group could react
for further elaboration. In addition, coupling of 2-
naphthylsulfinic acid sodium salt proceeded well,
Table 3. Scope of Sodium Sulfinates[a]
[a] Reaction conditions: 1a (0.2 mmol), RSO2Na (0.4 mmol), NiBr2 (10 mol%), PhCOOH (20 mol%) and Ag2CO3 (0.4 mmol)
in CHCl3 (1.0 mL) at 120 oC for 12 h under air. Isolated yields. Disulfonylated products were not detected.
3
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10.1002/adsc.201700290
Advanced Synthesis & Catalysis
furnishing the desired product 3h in 42% yield. Finally, activation occurs to form the Ar-NiII intermediate
we were pleased to find that aliphatic sodium sulfinate
such as sodium methanesulfinate was also reactive to
give the desired alkyl-aryl sulfone product 3i, albeit in
only 20% yield (see Table S5 in the Supporting
Information for additional results on this reaction).
The outcome was probably due to the low reactivity of
sodium methanesulfinate or the thermal instability of
the methylsulfonyl radical under the stated reaction
conditions.[11d,13b,16]
Finally, the PIP directing group can be removed
efficiently via the known three-step sequence,[11d]
affording the corresponding sulfonylated carboxylic
acids.
B.[17a] Simultaneously, the single-electron oxidation of
sodium sulfinate leads to the formation of sulfonyl
radical,[17b,c] which reacts with B to generate the NiIII
complex C.[17d,e] Subsequent C−SO2Ph reductive
elimination of C leads to the formation of the NiI
species D. The sulfonylated product 2a can be
obtained after protonation of D. Finally, the generated
NiI species is re-oxidized into the NiII species by
Ag2CO3 to complete the catalytic cycle. However, at
the current stage, the Ni(II)/Ni(IV) pathway could not
be excluded.
To shed light on the plausible reaction mechanism,
various control experiments were performed (Scheme
2). Firstly, we noted that benzenesulfinic
benzenesulfonic anhydride 4 was formed in the
reaction of amide 1a and PhSO2Na, which could also
be observed in the absence of either Ag2CO3 or NiBr2
under standard conditions (see the Supporting
Information). In addition, the reaction of 1a and (p-
Cl)PhSO2Na was completely inhibited when TEMPO
(2,2,6,6-tetramethyl-1-piperidinyloxy) was added.
The addition of BHT (2,6-di-tert-butyl-4-methyl-
phenol) and 1,1-diphenylethylene also decreased the
yield significantly (Scheme 2a). More importantly, a
sulfonyl radical was trapped by 1,1-diphenylethylene
in the presence or absence of amide 1a (Scheme 2a).
The results suggested the probable involvement of
radicals in the reaction. Furthermore, kinetic isotope
effect (KIE) experiments were conducted (Scheme 2b).
The reaction of 1a and [D5]-1a with PhSO2Na gave a
significant KIE of 4.0. Likewise, the KIE value of two
parallel reactions was calculated to be 2.9. These
results indicated that C-H cleavage of benzamide was
involved in the rate-determining step.
Scheme 3. Proposed Mechanism.
In summary, we have developed a Ni-catalyzed
auxiliary-assisted sulfonylation of C(sp2)–H bonds
with sodium sulfinates to afford various diaryl and
alkyl-aryl sulfones in modest to excellent yields. This
strategy has the advantages of using inexpensive Ni as
the catalyst and safe, air and moisture stable sodium
sulfinates as the sulfonylating agent, high
regioselectivity as well as broad substrate scope.
What’s more, based on our experimental results and
related precedents, a plausible mechanism for the
current sulfonylation is proposed.
Experimental Section
Typical Procedure
To a 35 mL pressure Schlenk tube were added 1a (48.1 mg,
0.2 mmol), NiBr2 (4.4 mg, 0.02 mmol), PhCOOH (4.9 mg,
0.04 mmol), PhSO2Na (65.7 mg, 0.4 mmol), Ag2CO3 (110.3
mg, 0.4 mmol) and CHCl3 (1.0 mL). The reaction was
stirred at 120 °C for 12 hours under air. Then the mixture
was cooled to room temperature, diluted with EtOAc and
filtered through a pad of celite, which was washed with
EtOAc. Evaporation of the organic solvent and purified by
preparative TLC on silica gel plates using petroleum
ether/EtOAc = 3:1 as the eluent to give the desired product
2a as a white foam (60.9 mg) in 80% yield.
Scheme 2. Control Experiments.
On the basis of the observations above and literature
precedents,[7c-e,17] especially the related work of
Chatani and Ge,[7c-e] a plausible Ni(I)/Ni(III)
mechanism was proposed in Scheme 3. First
complexation of benzamide 1a with a NiII species
affords the NiII intermediate A. Next C–H bond
Acknowledgements
Financial support from the National Natural Science Foundation
of China (Nos. 21672192 and 21472176) is gratefully
acknowledged.
4
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10.1002/adsc.201700290
Advanced Synthesis & Catalysis
References
2015, 80, 1269-1274; d) D. Zhang, X. Cui, Q. Zhang, Y.
Wu, J. Org. Chem. 2015, 80, 1517-1522; e) W.-H. Rao,
B.-B. Zhan, K. Chen, P.-X. Ling, Z.-Z. Zhang, B.-F. Shi,
Org. Lett. 2015, 17, 3552-3555.
[1] a) S. Patai, Z. Rappoport, C. J. M. Stirling, The
Chemistry of Sulfones and Sulfoxides, Wiley, New York,
1988; b) Q. A. Acton, Sulfones-Advances in Research
and Application, ScholarlyEditions, Atlanta, 2013.
[10] F. Wang, X. Yu, Z. Qi, X. Li, Chem. Eur. J. 2016, 22,
511-516.
[2] a) L. Ramberg, B. Bäcklund, Ark. Chim., Mineral Geol.
1940, 27, 1-50; b) S. C. Söderman, A. L. Schwan, J. Org.
Chem. 2012, 77, 10978-10984.
[11] Selected examples: a) Z. Wu, H. Song, X. Cui, C. Pi,
W. Du, Y. Wu, Org. Lett. 2013, 15, 1270-1273; b) H.-
W. Liang, K. Jiang, W. Ding, Y. Yuan, L. Shuai, Y.-C.
Chen, Y. Wei, Chem. Commun. 2015, 51, 16928-16931;
c) J. Liu, L. Yu, S. Zhuang, Q. Gui, X. Chen, W. Wang,
Z. Tan, Chem. Commun. 2015, 51, 6418-6421; d) W.-H.
Rao, B.-F. Shi, Org. Lett. 2015, 17, 2784-2787; e) S.
Liang, N.-W. Liu, G. Manolikakes, Adv. Synth. Catal.
2016, 358, 159-163; f) S. Liang, G. Manolikakes, Adv.
Synth. Catal. 2016, 358, 2371-2378; g) Y. Yang, W. Li,
C. Xia, B. Ying, C. Shen, P. Zhang, ChemCatChem 2016,
8, 304-307; h) J. Wei, J. Jiang, X. Xiao, D. Lin, Y. Deng,
Z. Ke, H. Jiang, W. Zeng, J. Org. Chem. 2016, 81, 946-
955; i) B. Du, P. Qian, Y. Wang, H. Mei, J. Han, Y. Pan,
Org. Lett. 2016, 18, 4144-4147; j) S. Liang, M. Bolte, G.
Manolikakes, Chem. Eur. J. 2017, 23, 96-100.
[3] M. Julia, J.-M. Paris, Tetrahedron Lett. 1973, 14, 4833-
4836.
[4] For recent reviews, see: a) N.-W. Liu, S. Liang, G.
Manolikakes, Synthesis 2016, 48, 1939-1973; b) S.
Shaaban, S. Liang, N.-W. Liu, G. Manolikakes, Org.
Biomol. Chem. 2017, 15, 1947-1955. For recent
examples, see: c) X.-S. Wu, Y. Chen, M.-B. Li, M.-G.
Zhou, S.-K. Tian, J. Am. Chem. Soc. 2012, 134, 14694-
14697; d) Q. Lu, J. Zhang, F. Wei, Y. Qi, H. Wang, Z.
Liu, A. Lei, Angew. Chem. 2013, 125, 7297-7300;
Angew. Chem. Int. Ed. 2013, 52, 7156-7159; e) X. Tang,
L. Huang, Y. Xu, J. Yang, W. Wu, H. Jiang, Angew.
Chem. 2014, 126, 4289-4292; Angew. Chem. Int. Ed.
2014, 53, 4205-4208; f) Y. Xi, B. Dong, E. J. McClain,
Q. Wang, T. L. Gregg, N. G. Akhmedov, J. L. Petersen,
X. Shi, Angew. Chem. 2014, 126, 4745-4749; Angew.
Chem. Int. Ed. 2014, 53, 4657-4661.
[12] O. Saidi, J. Marafie, A. E. W. Ledger, P. M. Liu, M. F.
Mahon, G. Kociok-Köhn, M. K. Whittlesey, C. G. Frost,
J. Am. Chem. Soc. 2011, 133, 19298-19301.
[13] a) A. Yokota, N. Chatani, Chem. Lett. 2015, 44, 902-
904; b) V. P. Reddy, R. Qiu, T. Iwasaki, N. Kambe, Org.
Biomol. Chem. 2015, 13, 6803-6813.
[5] Selected reviews: 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) T. W. Lyons, M.
S. Sanford, Chem. Rev. 2010, 110, 1147-1169; c) X.-X.
Guo, D.-W. Gu, Z. Wu, W. Zhang, Chem. Rev. 2015,
115, 1622-1651; d) C. Shen, P. Zhang, Q. Sun, S. Bai,
T. S. Andy Hor, X. Liu, Chem. Soc. Rev. 2015, 44, 291-
314.
[14] Selected recent publications: a) L.-B. Zhang, X.-Q. Hao,
S.-K. Zhang, Z.-J. Liu, X.-X. Zheng, J.-F. Gong, J.-L.
Niu, M.-P. Song, Angew. Chem. 2015, 127, 274-277;
Angew. Chem. Int. Ed. 2015, 54, 272-275; b) X.-X.
Zheng, C. Du, X.-M. Zhao, X. Zhu, J.-F. Suo, X.-Q. Hao,
J.-L. Niu, M.-P. Song, J. Org. Chem. 2016, 81, 4002-
4011; c) S.-L. Liu, X.-H. Li, T.-H. Shi, G.-C. Yang, H.-
L. Wang, J.-F. Gong, M.-P. Song, Eur. J. Org. Chem.
DOI: 10.1002/ejoc.201700147.
[6] Selected recent reviews: a) G. Rouquet, N. Chatani,
Angew. Chem. 2013, 125, 11942-11959; Angew. Chem.
Int. Ed. 2013, 52, 11726-11743; b) S. Z. Tasker, E. A.
Standley, T. F. Jamison, Nature, 2014, 509, 299-309; c)
L. C. Misal Castro, N. Chatani, Chem. Lett. 2015, 44,
410-421; d) B.-B. Zhan, B. Liu, F. Hu, B.-F. Shi, Chin.
Sci. Bull. 2015, 60, 2907-2917.
[15] Selected examples: a) Q. Zhang, K. Chen, W. Rao, Y.
Zhang, F.-J. Chen, B.-F. Shi, Angew. Chem. 2013, 125,
13833-13837; Angew. Chem. Int. Ed. 2013, 52, 13588-
13592; b) F.-J. Chen, S. Zhao, F. Hu, K. Chen, Q. Zhang,
S.-Q. Zhang, B.-F. Shi, Chem. Sci. 2013, 4, 4187-4192;
c) Y.-H. Liu, Y.-J. Liu, S.-Y. Yan, B.-F. Shi, Chem.
Commun. 2015, 51, 11650-11653; d) Y.-J. Liu, Y.-H.
Liu, X.-S. Yin, W.-J. Gu, B.-F. Shi, Chem. Eur. J. 2015,
21, 205-209.
[7] Selected examples: a) H. Shiota, Y. Ano, Y. Aihara, Y.
Fukumoto, N. Chatani, J. Am. Chem. Soc. 2011, 133,
14952-14955; b) K. Muto, J. Yamaguchi, K. Itami, J. Am.
Chem. Soc. 2012, 134, 169-172; c) Y. Aihara, N. Chatani,
J. Am. Chem. Soc. 2013, 135, 5308-5311; d) Y. Aihara,
N. Chatani, J. Am. Chem. Soc. 2014, 136, 898-901; e) X.
Wu, Y. Zhao, H. Ge, J. Am. Chem. Soc. 2014, 136, 1789-
1792; f) W. Song, S. Lackner, L. Ackermann, Angew.
Chem. 2014, 126, 2510-2513; Angew. Chem. Int. Ed.
2014, 53, 2477-2480.
[16] H. H. Thoi, M. Iino, M. Matsuda, Macromolecules
1979, 12, 338-339.
[17] a) K. Yang, Y. Wang, X. Chen, A. A. Kadi, H.-K. Fun,
H. Sun, Y. Zhang, H. Lu, Chem. Commun., 2015, 51,
3582-3585; b) H.-S. Li, G. Liu, J. Org. Chem. 2014, 79,
509-516; c) N. Taniguchi, J. Org. Chem. 2015, 80, 7797-
7802; d) S. Biswas, D. J. Weix, J. Am. Chem. Soc. 2013,
135, 16192-16197; e) J. Breitenfeld, J. Ruiz, M. D.
Wodrich, X. Hu, J. Am. Chem. Soc. 2013, 135, 12004-
12012.
[8] X. Zhao, E. Dimitrijević, V. M. Dong, J. Am. Chem. Soc.
2009, 131, 3466-3467. For review on the synthesis of
sulfones via C-H functionalization, see ref. 4b.
[9] a) Y.-H. Xu, M. Wang, P. Lu, T.-P. Loh, Tetrahedron
2013, 69, 4403-4407; b) B. Ge, D. Wang, W. Dong, P.
Ma, Y. Li, Y. Ding, Tetrahedron Lett. 2014, 55, 5443-
5446; c) Y. Xu, P. Liu, S.-L. Li, P. Sun, J. Org. Chem.
5
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Advanced Synthesis & Catalysis
COMMUNICATION
Nickel-Catalyzed Sulfonylation of C(sp2)–H Bonds
with Sodium Sulfinates
Adv. Synth. Catal. Year, Volume, Page – Page
Shuang-Liang Liu,a Xue-Hong Li,a Shu-Sheng
Zhang,a Sheng-Kai Hou,a Guang-Chao Yang,a Jun-
Fang Gong,a,* and Mao-Ping Song a,*
6
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