Mn(III)-mediated regioselective synthesis of (: E)-vinyl sulfones from sodium sulfinates and nitro-olefins

Article abstract of DOI:10.1039/c6ra17842a

An efficient Mn(iii)-mediated coupling reaction of sodium sulfinates with nitro-olefins has been developed, this reaction proceeds in mild and open-flask conditions to afford (E)-vinyl sulfones with high regioselectivities and in good to excellent yields. The control experiments revealed that this transformation could involve a radical process.

Full text of DOI:10.1039/c6ra17842a

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Mn(III)-Mediated Regioselective Synthesis of (E)-Vinyl Sulfones
from Sodium Sulfinates and Nitro-olefins
Received 00th January 20xx,
Accepted 00th January 20xx
Gang Nie, Xiaocong Deng, Xue Lei, Qinquan Hu, and Yunfeng Chen*
DOI: 10.1039/x0xx00000x
www.rsc.org/
relatively stable, simple to be obtained by Henry reaction from
aldehyde and nitromethane, which have been widely used to
synthesize useful organic molecules. In some cases, the nitro-
olefins are equivalent to alkyne synthon by the elimination of
HNO2 or an oxidative dehydrogenation process. For example,
nitro-olefins are good partners for the synthesis of NH-1,2,3-
triazoles and NO2-substituted 1,2,3-triazoles.11
An efficient Mn(III)-mediated coupling reaction of sodium
sulfinates with nitro-olefins has been developed, this reaction
proceeds in a mild and open-flask condition to afford (E)-vinyl
sulfones with high regioselectivities and in good to excellent
yields. The control experiments revealed that this transformation
could involve a radical process
.
Vinyl sulfones are important structural synthons in the
synthetic organic chemistry, which are good Michael acceptors
and also easy to participate in cycloaddition reactions.1
Nowadays, its derivatives have also shown a widely biological
and pharmacological activities.2 So far, many conventional
approaches for the synthesis of vinyl sulfones have been
established, including the oxidation of the corresponding
sulfides,3 β-elimination of selenosulfones and halosulfones,4
and addition of sulfonyl chloride to alkynes/alkenes.5 In recent
years, sodium sulfinate and sulfonyl hydrazine have been
utilized to react with different partners for synthesis of vinyl
sulfones, probably due to their good stability and ease of
handling.6 The direct addition of sodium sulfinates to terminal
aromatic alkynes7 and propiolic acid8 in the presence of Cu or
Pd catalysts could give vinyl sulfones with high yields and
regioselectivities. At the same time, alkenes are also good
reaction partners to produce vinyl sulfones via oxidative
coupling reactions with sodium sulfinates (Scheme 1).9 For
instance, Nair’s group reported one-pot synthesis of vinyl
sulfones via CAN-mediated reaction of aryl sulfinates and
Nair's work:
NaI, CAN, CH3CN, Ar, rt;
Kuhakarn's work:
KI, PhI(OAc)2, CH3CN, rt;
KI, NaIO4, AcOH, MeCN, rt;
KI, TBHP, DMSO/AcOH, rt;
Das's work:
Lei's work:
Yang and Wang's work:
I2, H2O, rt
O
S R
O
conditions
Ar
RSO2Na
+
Ar
Guo's work: KI, CuO, DMSO, air, 100 oC;
Kuhakarn's work: KI, PhI(OAc)2, CH3CN, rt;
Mao and Shi's work: I2, TBHP, toluene, 90 oC;
Jiang's work: K2CO3, DMSO, 100 oC;
O
S R
O
COOH
+
conditions
Ar
RSO2Na
Ar
Ar
Yadav's work
O
S R
O
Ag/K2S2O8
N2, rt
NO2
Ar
RSO Na
+
2
our work
O
S R
O
alkenes.9a Lately, KI/PhI(OAc)2 , KI/NaIO49c, KI/TBHP9d together
9b
Mn(III)
NO2
Ar
RSO2Na
+
9e
with stoichiometric I2 and other methods9k-m have also been
Ar
open-flask
developed by different groups. The cinnamic acids can
undergo decarboxylation in many reaction systems.10 Guo’s
Scheme 1. Synthesis of vinyl sulfones from sodium sulfinates and
alkenes.
group designed
a
copper-catalyzed aerobic oxidative
decarboxylative sulfonylation reaction to synthesize vinyl
sulfones by using cinnamic acids and sodium sulfinates as the
starting materials.10c Interestingly, Jiang and co-workers
revealed a transition metal-free base-promoted variant, which
made this transformation greener.10d Nitro-olefins are
In fact, Yadav’s group reported a silver-catalyzed coupling
reaction of nitro-olefins and sodium sulfinates in the presence
of oxidant and under nitrogen atmosphere.12 Encouraged by
this work, we wanted to develop other methods, especially
cheaper metal salts and simpler operation to make this
transformation more applicable. Herein, we reported an
efficient synthesis of (E)-vinyl sulfones by Mn(III)-mediated
coupling reaction of nitro-olefins with sodium sulfinates under
air.
*School of Chemistry and Environmental Engineering, Wuhan Institute of
Technology, Wuhan 430073, People’s Republic of China E-mail: yfchen@wit.edu.cn
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See DOI:
10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Table 1. Optimization of the Reaction Conditions a
result (entries 10 and 11), which revealed that the silver salt
system could not work in this case. To further improve the
yield of 3a, different reaction temperatures were set, the yield
of the expected product 3a increased to 92% when the
reaction temperature reached up to 100 oC (entries 12-16).
Attempts to reduce the amount of Mn(OAc)3 failed, and
Mn(OAc)3/K2S2O8 system gave inferior result (entries 17-19).
Meanwhile, various solvents were examined, which indicated
that the reaction performed in DMF was significantly better
than those in toluene, AcOH, EtOH, DMSO or H2O (entries 20-
24). Under argon atmosphere, the yield of 3a was similar to
Entry
Oxidant
Oxidant(equiv)
Solvent
Temp(oC) Yieldc(%)
1
2
I2
KI/TBHP
2.5
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
toluene
AcOH
EtOH
DMSO
H2O
rt
rt
trace
trace
16
0.2/2.5
3
TBHP
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
0.2/2.5
3
rt
the open flask condition (entry 25)
.
4
DTBP
rt
19
5
K2S2O8
rt
14
Table 2. Substrate Scope for the Synthesis of Various Vinyl
Sulfonesa
6
Fe(NO3)3
FeCl3
rt
17
7
rt
13
O
Mn(OAc)3
NO2
RSO2Na
S
R
+
Ar
Ar
DMF 100oC air
8
CuSO4
rt
trace
38
O
9
Mn(OAc)3
AgNO3
rt
O
O
O
S
S
R
S
Cl
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25d
rt
ndb
nd
O
O
O
R
Br
R
AgNO3/ K2S2O8
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3/K2S2O8
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
rt
R = H, 3i, 88%
R = Me, 3j, 86%
R = OMe, 3k, 85%
R = Cl, 3l, 76%
R = H, 3a, 92%
R = Me, 3b, 92%
R = OMe, 3c, 89%
R = Cl, 3d, 73%
R = Br, 3e, 78%
R = H, 3f, 76%
R = Me, 3g, 75%
R = Cl, 3h, 74%
rt
46
3
40
60
80
100
100
100
100
100
100
100
100
100
100
59
O
O
S
S
O
CH3
CH3
3
65
O
S
O
O
CH3
OH
3
77
O
3r, 56%
3s, 41%
R
O
S
O
S
3
92
R = H, 3m, 86%
R = Me, 3n, 90%
R = OMe, 3o, 94%
R = Cl, 3p, 75%
R = Br, 3q, 81%
F
OMe
O
0.2
2
33
O
MeO
R
R = Me, 3u, 92%
R = OMe, 3v, 90%
84
3t, 92%
0.2/3
3
56
O
S
R1
O
S
R1 = H, R2 = NO2, R3 = H; 3x, <5%
R1 = NO2, R2 = H, R3 = H, 3y, <5%
R1 = H, R2 = F, R3 = H, 3z, <5%
nd
R3
O
O
OMe
3
47
R2
3w, 93%
aReaction conditions: nitroolefins (0.3 mmol), sodium
sulfinates (0.6 mmol, 2 equiv), Mn(OAc)3 (0. 9 mmol, 3 equiv),
3
14
3
45
DMF (5mL), 100°C, air.
bIsolated yield.
3
37
With the optimized protocol in hand, we further examined the
scope and limitation of this coupling reaction between
different nitro-olefins and sodium sulfinates, and the results
3
DMF
90
aReaction conditions: nitro-benzeneolefin (1a) (0.3 mmol),
sodium benzenesulfinate (2a) (2 equiv, 0.6 mmol), solvent (5
mL), 8 h, air. bnd, not detected, cIsolated yield, dArgon
atmosphere.
are summarized in Table
2. Nitro-olefins with electron-
donating functional group such as OMe, Me have higher yield
than those with electron-drawing group such as Cl, Br. For
instance, Nitro-olefins with electron-donating functional group
gave the corresponding product in 86-93% yields (3a-c, 3i-k,
3m-o, 3u-3v, 3w). Instead, Nitro-olefins with electron-drawing
group gave 73-81% yields of the products (3d-e, 3h, 3l, 3p-q).
It is noteworthy that sodium sulfinates with electron-donating
groups and withdrawing groups have no significant influence
on the transformation (3v, 3t). Furthermore, acid-sensitive
furanyl-substituted nitro-olefin was also suitable substrate to
Our studies began by examining the reaction between nitro-
olefin (1a) and sodium benzenesulfinate (2a) in the presence
of a stoichiomertic I2 in DMF at room temperature under air
(
Table 1, entry 1), the corresponding product 3a was not
observed at all, and KI/TBHP system gave the same result too
entry 2). However, TBHP, DTBP and K2S2O8 could promote this
(
reaction despite low yields (entries 3-5). Then, other metal
salts oxidants such as Fe(NO3)3, FeCl3, Mn(OAc)3, and CuSO4
react with sodium sulfinate
，the furanyl-substituted vinyl
were tested, Mn(OAc)3 showed superior reactivity towards this sulfone (3s) was obtained in 41% isolated yield. Unfortunately,
coupling reaction and the yield of 3a increased to 38% (entries nitro-olefins with NO2 group couldn’t give the corresponding
6-9). By contrast with Yadav’s protocol, AgNO3 was also products (3x-z).13
introduced into this reaction, but the product 3a was not To gain insights into mechanism of the reaction, nitro-olefin
observed at all, AgNO3/K2S2O8 system also gave the same
(
1a) and sodium benzenesulfinate (2a) reacted in the presence
2 | J. Name., 2012, 00, 1-3
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Mn(II)
Mn(III)
PhSO2Na
of 2,2,6,6-tetramethylpiperidinooxy (TEMPO, 3eq) which is a
radical scavenger under standard condition Scheme ).
NO2
Ph
(
2
PhSO2
However, 3a was no detected, which implied that this reaction
could involve a radical process. Under oxygen atmosphere, the
reaction only gave the desired product 3a, while assumed
oxidative product 4a was not detected, which showed that
A
NO2
SO2Ph
SO2Ph
Ph
Ph
B
C
Mn(III) could not promote
process.14
a metal-catalyzed oxidization
NO2
In summary, we have developed an efficient Mn(III)-mediated
synthesis of (E)-vinyl sulfones through coupling reactions of
sodium sulfinates with nitro-olefins. The synthetic method
presented many advantages such as cheap metal, simple
operation, easily available substrate, and good yields, which is
promising for practical applications in relevant industry and
manufacture in the future.
Scheme 2. Control Experiments
We are grateful to the National Natural Science Foundation of
China (21002076), the Scientific Research Foundation for the
Returned Overseas Chinese Scholars for financial support. We
also thank NO.CX2015151, supported by Graduate Innovative
Fund of Wuhan Institute of Technology.
Furthermore, in order to reveal the role of the nitro group in
this reaction, we reconsidered the reaction between styrene
and sodium sulfinates, most of which need I2 or I-/oxidants,
and Lei disclosed that I2 system involve a HI elimination similar
Notes and references
1. (a) A. K. Musser, P. L. Fuchs, J. Org. Chem. 1982, 47, 3121; (b)
R. V. C. Carr, R. V. Williams, L. A. Paquette, J. Org. Chem.
1983, 48, 4976; (c) W. A. Kinney, G. D. Crouse, L. A.
Paquette, J. Org. Chem. 1983, 48, 4986; (d) T. Llamas, R. G.
to the β-hydride elimination of transition metals process to
achieve alkenylation for the formation of vinyl sulfones.9h Then
the reactions between styrene and sodium sulfinates in the
presence of Mn(OAc)3 were investigated. Under our standard
Arrayas, J. C. Carretero, Org. Lett. 2006,
Liang, M. C Tong, C. J. Wang, Adv Synth Catal. 2009, 351
3101; (f) S. Dey, D. Datta, T. Pathak, Synlett. 2011, 2521; (g)
D. Sahu, S. Dey, T. Pathak, B. Ganguly, Org. Lett. 2014, 16
8, 1795; (e) G.
,
condition, the reaction between styrene (5) and sodium
,
sulfinates in the presence of three equivalent or catalytic
amount of Mn(OAc)3 induce the 100% conversion of styrene,
however, the desired vinyl sulfone 3a was detected in less
than 10% yield, most of styrene was polymerized. This result
showed that Mn(III) could not react with the carbon radical,
2100; (h) J. R. Bull, K. Bischofberger, J. Chem. Soc., Perkin
Trans. 1 1991, 2859; (i) T. Llamas, R. G. Arrayas, J. C.
Carretero, Synthesis-Stuttgart. 2007, 950; (j) J. K. Laha,
Chem Nat Compd. 2010, 46, 254; (k) J. Yang, W. Yin, R.
Liu, C. Chu, Chin. J. Chem. 2012, 30, 2786; (l) M. I.
Pleshchev, V. V. Kachala, A. S. Goloveshkin, I. S.
Bushmarinov, V. V. Kuznetsov, D. V. Khakimov, N. N.
Makhova, Mendeleev Commun. 2013, 23, 271; (m) V. A.
Vasin, V. V. Razin, E. V. Bezrukova, D. Y. Korovin, P. S.
Petrov, N. V. Somov, Russ. J. Org. Chem. 2015, 51, 1144.
2. (a) S. Liu, R. P. Hanzlik, J. Med. Chem. 1992, 35, 1067; (b) J. T.
Palmer, D. Rasnick, J. L. Klaus, D. Brömme, J. Med. Chem.
1995, 38, 3193; (c) W. R. Roush, S. L. Gwaltney II, J. Cheng,
K. A. Scheidt, J. H. McKerrow, E. Hansell, J. Am. Chem. Soc.
1998, 120, 10994; (d) J. J. Reddick, J. Cheng, W. R. Roush,
the successively β-hydride elimination process didn’t exist. By
contrast, a potential elimination of nitro radical should be
involved during the coupling of nitro-olefins with sodium
sulfinates.
On the basis of the results described above and previous
literature reports,12, 15 a plausible mechanism was proposed in
Scheme 3. Firstly, a radical
oxidation of sodium sulfinate by Mn(III) under heating. Next,
intermediate was generated through the trans-addition of
to the nitro-olefin. Then, intermediate eliminated a nitro
radical to give product . The nitro radical may be quenched
A was initially formed through the
B
A
Org. Lett. 2003,
5
Chen, S. Yao, Org. Lett. 2003,
, 1967; (e) G. Wang, U. Mahesh, G. Y. J.
, 737; (f) B. R. Shenai, B. J.
B
5
C
Lee, A. Alvarez-Hernandez, P. Y. Chong, C. D. Emal, R. J.
Neitz, W. R. Roush, P. J. Rosenthal, Antimicrob. Agents
Chemother. 2003, 47, 154; (g) B. A. Frankel, M. Bentley, R.
by other radical species or Mn(OAc)3, that’s the reason why
too much excess amount of Mn(OAc)3 was needed.
G. Kruger, D. G. McCafferty, J. Am. Chem. Soc. 2004, 126
3404; (h) D. C. Meadows, T. Sanchez, N. Neamati, T. W.
North, J. Gervay-Hague, Bioorg. Med. Chem. 2007, 15
,
Scheme 3. A plausible mechanism
,
1127; (i) M. Uttamchandani, K. Liu, R. C. Panicker, S. Yao,
Chem. Commun. 2007, 1518; (j) K. Steert, I. El-Sayed, P.
Vander Veken, A. Krishtal, C. Van Alsenoy, G. D. Westrop, J.
This journal is © The Royal Society of Chemistry 20xx
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C. Mottram, G. H. Coombs, K. Augustyns, A. Haemers, 10. (a) R. Guo, Q. Gui, D. Wang, Z. Tan, Catal. Lett. 2014, 144
Bioorg. Med. Chem. Lett. 2007, 17, 6563; (k) R. Ettari, E. 1377; (b) B. V. Rokade, K. R. Prabhu, J. Org. Chem. 2014,
Nizi, M. E. D. Francesco, M.-A. Dude, G. Pradel, R. Vi ík, T.
,
79, 8110; (c) Q. Jiang, B. Xu, A. Zhao, Y. Zhao, Y. Li, N. He,
C. Guo, J. Org. Chem. 2014, 79, 7372; (d) Y. Xu, X. Tang,
W. Hu, W. Wu, H. Jiang, Green Chem. 2014, 16, 3720; (e)
P. Katrun, S. Hlekhlai, J. Meesin, M. Pohmakotr, V.
Reutrakul, T. Jaipetch, D. Soorukram, C. Kuhakarn, Org.
Biomol. Chem. 2015, 13, 4785; (f) H. Li, G. Liu, J. Org.
Chem. 2014, 79, 509; (g) J. Chen, J. Mao, Y. Zheng, D. Liu,
č
Schirmeister, N. Micale, S. Grasso, M. Zappalà, J. Med.
Chem. 2008, 51, 988; (l) S. Y. Woo, J. H. Kim, M. K. Moon,
S.-H. Han, S. K. Yeon, J. W. Choi, B. K. Jang, H. J. Song, Y. G.
Kang, J. W. Kim, J. Lee, D. J. Kim, O. Hwang, K. D. Park, J.
Med. Chem. 2014, 57, 1473.
3. (a) A. A. Lindén, L. Krüger, J. Bäckvall, J. Org. Chem. 2003, 68
5890; (b) F. G. Gelalcha, B. Schulze, J. Org. Chem. 2002, 67
8400; (c) M. Matteucci, G. Bhalay M. Bradley, Org. Lett.
2003, , 235.
4. (a) J. Sinnreich, M. Asscher, J. Chem. Soc. Perkin Trans. 1
1972, 1543; (b) P. B. Hopkins, P. L. Fuchs, J. Org. Chem.
1978, 43, 1208; (c) R. V. C. Carr, R. V. Williams, L. A.
Paquette, J. Org. Chem. 1983, 48, 4976. (d) F. E. K. Kroll, R.
Morphy, D. Rees, D. Gani, Tetrahedron Lett. 1997, 38, 8573.
5. (a) L. M. Harwood, M. Julia, G. Le Thuillier, Tetrahedron.
,
,
G. Rong, H. Yan, C. Zhang, D. Shi, Tetrahedron. 2015, 71
5059; (h) J. Gao, J. Lai, G. Yuan, RSC. Adv. 2015, 5, 66723.
,
11. For selected examples, see: (a) S. Sengupta, H. Duan, W.
Lu, J. L. Petersen, X. Shi, Org. Lett. 2008, 10, 1493; (b) B.
Quiclet-Sire, S. Z. Zard, Synthesis, 2005, 3319; (c) X.-J.
Quan, Z.-H. Ren, Y.-Y. Wang, Z.-H. Guan, Org. Lett. 2014,
16, 5728; (d) Y. Chen, G. Nie, Q. Zhang, S. Ma, H. Li, Q. Hu,
Org. Lett. 2015, 17, 1118; (e) Q. Hu, Y. Liu, X. Deng, Y. Li ,
Y. Chen, Adv. Synth. Catal. 2016, 358, 1689.
5
12. T. Keshari, R. Kapoorr, L. D. S. Yadav, Eur. J. Org. Chem.
2016, 2695.
13. For some examples, see: (a) H. Tian, A. Cao, L. Qiao, A. Yu ,
J. Chang, Y. Wu, Tetrahedron. 2014, 70, 9107; (b) W.
Zhang, J. Xie, B. Rao, M. Luo, J. Org. Chem. 2015, 80, 3504;
1980, 36, 2483; (b) S. Zhu, C. Qin, G. Xu, Q. Chu,
Tetrahedron Lett. 1998, 39, 5265; (c) T. G. Back, S. Collins, J.
Org. Chem. 1981, 46, 3249; (d) V. Nair, A. Augustine, S. B.
Panicker, T. D. Suja, S. Mathai, Res. Chem. Intermed. 2003,
29, 213; (e) H. Qian, X. Huang, Synlett. 2001, 1913.
(c) F. Zhao, B. Li, H. Huang ,G.-J. Deng, RSC. Adv. 2016, 6,
13010.
6. (a) X. Li, X. Xu, C. Zhou, Chem. Commun. 2012, 48, 12240;
(b) X. Q. Li, X. Shi, M. Fang, X. Xu, J. Org. Chem. 2013, 78,
14. (a) Q. Lu, J. Zhang, G. Zhao, Y. Qi , H. Wang, A. Lei, J. Am.
Chem. Soc. 2013, 135, 11481; (b) W. Wei, C. Liu, D. Yang,
9499; (c) X. Li, Y. Xu, W. Wu, C. Jiang, C. Qi, H. Jiang,
Chem. Eur. J. 2014, 20, 7911; (d) G. Rong, J. Mao, H. Yan,
Y. Zheng, G. Zhang, J. Org. Chem. 2015, 80, 4697; (e) S. Li,
J. Wen, J. You, Y. Suo, H. Wang, Chem. Comm. 2013, 49
,
10239; (c) R. Chawla, A. K. Singh, L. D. S. Yadav, Eur. J.
Org. Chem. 2014, 2032; (d) A. K. Singh, R. Chawla, L. D. S.
Yadav, Tetrahedron. Lett. 2014, 55, 4742; (e) W Wei, J.
Wen, D. Yang, M. Wu, J You, H. Wang, Org. Biomol. Chem.
2014, 12, 7678; (f) B. Sreedhar V. Rawat, Synlett, 2012,
413, (g) A. K. Singh, R. Chawla, L. D. S. Yadav, Tetrahedron.
Letters. 2014, 55, 2845; (h) N. Samakkanad, P. Katrun, T.
Techajaroonjit, S. Hlekhlai, M. Pohmakotr, V. Reutrakul,
T. Jaipetch, D. Soorukram, C. Kuhakarn, Synthesis. 2012,
44, 1693.
X. Li, F. Yang, Y. Wu, Org. Chem. Fron. 2015, 2, 1076.
7. (a) G. M. Shelke, V. K. Rao, K. Pericherla, A. Kumar, Synlett.
2014, 25, 2345; (b) Y. Xu, J. Zhao, X. Tang, W. Wu, H.
Jiang, Adv Synth Catal. 2014, 356, 2029; (c) N. Taniguchi,
Synlett. 2012, 23, 1245; (d) N. Taniguchi, Tetrahedron.
2014, 70, 1984; (e) W. Wei, J. Li, D. Yang, J. Wen, Y. Jiao,
J. You, H. Wang, Org. Biomol. Chem. 2014, 12, 1861; (f) Q.
Xue, Z. Mao, Y. Shi, H. Mao, Y. Cheng, C. Zhu,
Tetrahedron Lett. 2012, 53, 1851; (g) J. L. G. Ruano, J.
Alemán, C. G. Paredes, Org. Lett. 2006, 8, 2683
15. For some Mn(III)-assisted radical reactions, see: (a) X.-J.
Mu, J.-P. Zou, Q.-F. Qian, W. Zhang, Org. Lett. 2006, 8,
8. (a) G. Rong, J. Mao, H. Yan, Y. Zheng, G. Zhang, J. Org.
Chem. 2015, 80, 7652; (b) J. Meesin, P. Katrun, V.
Reutrakul, M. Pohmakotr, D. Soorukram, C. Kuhakarn,
Tetrahedron. 2016, 72, 1440.
5291; (b) W. Xu, J.-P. Zou, W. Zhang, Tetrahedron. Lett.
2010, 51, 2639; (c) J.-F. Xue, S.-F. Zhou, Y.-Y. Liu, X. Pan,
J.-P. Zou, O. T. Asekun, Org. Biomol. Chem. 2015, 13
,
9. (a) V. Nair, A. Augustine, T. G. George, L. G. Nair,
Tetrahedron. Lett. 2001, 42, 6763; (b) P. Katrun, S.
Chiampanichayakul, K. Korworapan, M. Pohmakotr, V.
Reutrakul, T. Jaipetch, C. Kuhakarn, Eur. J. Org. Chem.
2010, 5633; (c) N. Kamigata, H. Sawada, M. Kobayashi, J.
Org. Chem. 1983, 48, 3793; d) N. Taniguchi, Synlett. 2011,
1308; (e) V. Nair, A. Augustine, T. D. Suja, Synthesis. 2002,
2259; (f) B. Das, M. Lingaiah, K. Damodar, N. Bhunia,
Synthesis. 2011, 2941; (g) T. Sawangphon, P. Katrun, K.
Chaisiwamongkhol, M. Pohmakotr, V. Reutrakul, T.
Jaipetch, D. Soorukram, C. Kuhakarn, Synth. Commun.
2013, 43, 1692; (h) S. Tang, Y. Wu, W. Liao, R. Bai, C. Liu,
A. Lei, Chem. Commun. 2014, 50, 4496; (i) N. Zhang, D.
4896; (d) L. Li, J.-J. Wang, G.-W. Wang, J. Org. Chem.
2016, 81, 5433; (e) T. Kagayama, A. Nakano, S. Sakaguchi,
Y. Ishii, Org. Lett. 2006, 8, 407.
Yang, W. Wei, L. Yuan, Y. Cao, H. Wang, RSC. Adv. 2015, 5,
37013; (j) Y.-C. Luo, X.-J. Pan, G.-Q. Yuan, Tetrahedron.
2015, 71, 2119; (k) Q. Xue, Z. Mao, Y. Shi, H. Mao, Y.
Cheng, C. Zhu, Tetrahedron. Lett. 2012, 53, 1851; (l) R.
Chawla, R. Kapoor, A. K. Singh, L. D. S. Yadav, Green
Chem. 2012, 14, 1308; (m) S. Liang, R.-Y. Zhang, G. Wang,
S.-Y. Chen, X.-Q. Yu, Eur. J. Org. Chem. 2013, 7050.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6RA17842A
O
S
Mn(OAc)3
NO2
RSO2Na
+
R
Ar
Ar
DMF, 100 oC
O
23 examples
up to 93% yields
A new efficient Mn(III)-mediated coupling reaction of sodium sulfinates with nitro-olefins is described.
open-flask condition