3
protocol. In the case of aliphatic enol acetates and sodium
sulfinates the reaction did not work to produce the expected β-
keto sulfones. This is possibly because in the case of aliphatic
enol acetates far less stable alkyl free radicals are formed after
the attack of the sulfony radical on the aliphatic enol acetates as
compared to the benzyl free radicals formed in the case of
aromatic enol acetates. As demonstrated by the exclusive
formation of products 3a-l (Table 2), the present sulfonylation
reaction is highly regioselective.
3014; (i) Zhu, Y. P.; Liu, M. C.; Jia, F. C.; Yuan, J. J.; Gao, Q.
H.; Lian, M.; Wu, A. X. Org. Lett. 2012, 14, 3352: (j) Varma, A.
K.; Sukla, S. P.; Singh, J.; Rustagi, V. J. Org. Chem. 2011, 76,
670; (k) Zora, M.; Kivrak, A.; Yazici, C. J. Org. Chem. 2011,
6, 6706; (l) Lamani, M.; Prabhu, K. R. J. Org. Chem. 2011, 76,
7978; (m) Li, Y. X.; Ji, K. G.; Wang, H, X.; Ali, S.; Liang, Y. M.
J. Org. Chem. 2011, 76, 744.
(a) Yusubov, M. S.; Zhdenkin, V. Resource-Efficient Tech. 2015,
, 49; (b) Zheng, Z.; Zheng, D.; Negrerie, Y.; Zhao, K. Sci.
China: Chem. 2014, 57, 189; (c) Guo, Z.; Liu, B.; Zhang, Q.-H.;
Deng, W.-P.; Wang, Y.; Yang, Y.-H. Chem. Soc. Rev. 2014, 43,
5
7
2
.
1
3
(
1
480; (d) Uyanik, M.; Ishihara, K. ChemCatChem, 2012, 4, 177;
e) Zhang, Y.; Cui, X.-J.; Shi, F.; Deng, Y.-Q.; Chem. Rev. 2012,
12, 2467; (g) Xu, K.; Hu, Y.-B.; Zhang, S.; Zha, Z.-G.; Wang,
On the basis of the above observations and the literature
4,7,15
reports,
a plausible mechanism for the formation of β-keto
sulfones 3 is depicted in Scheme 2. Initially, molecular iodine
reacts with sodium sulfinate 2 to give sulfonyl iodide 4, which
undergoes homolysis to generate sulfonyl radical 5 and iodine
radical. The addition of 5 to arylenol acetate 1 forms radical
intermediate 6. The iodine radical combines with 6 to give
intermediate 7, which undergoes hydrolysis to afford the desired
β-keto sulfones 3 through the intermediate 7.
Z.-Y. Chem. Eur. J. 2012, 18, 9793; (h) Wang, C.; Yang, J.;
Cheng, X.; Li, E.; Li Y.; Tetrahedron Lett. 2012, 53, 4402; (i)
Kumar, A.; Wang, Y.; Zhu, D.-P.; Tang, L.; Wang, Z.-y.; Angew.
Chem. Int. Ed. 2011, 50, 8917; (j) Zhdankin, V. V. J. Org. Chem.
2
011, 76, 1185; (k) Merritt, E. A.; Olofsson, B. Angew. Chem.
Int. Ed. 2009, 48, 9052; (l) Zhdankin, V. V.; Stang, P. J. Chem.
Rev. 2008, 108, 5299; (m) P. J. Stang, V. V. Zhdankin, Chem.
Rev. 1996, 96, 1123; (n) V. V. Zhdankin, P. J. Stang, Chem. Rev.
2
002, 102, 2523.
(a) Zhao, X.; Li, T.; Zhanga, L.; Lu, K. Org. Biomol. Chem.
016, 14, 1131; (b) Sun, J.; Qiu, J.-K.; Zhu, Y.-L.; Guo, C.; Hao,
3
.
2
W.-J.; Jiang, B.; Tu, S.-J. J. Org. Chem. 2015, 80, 68217; (c)
Lin, Y.-m.; Lu, G.-p.; Cai, C.; Yi, W.-b. Org. Chem. 2015, 80,
8217; (d) Singh, R.; Allam, B. K.; Singh, N.; Kumari, K.; Singh,
S. K.; Singh K. N. Org. Lett. 2015, 17, 2656; (e) Zhao, X.;
Zhang, L.; Lu, X.; Li, T.; Lu, K. J. Org. Chem. 2015, 80, 2918;
O
S
2
O
S
O
S
I2
R2
R2
R2
I
I
ONa
NaI
4 O
AcO 5 O
(
f) Kang, X.; Yan, R.; Yu, G.; Pang, X.; Liu, X.; Li, X.; Xiang,
I2, 1, CH CN/H O (4:1)
R1
1
L.; Huang, G. J. Org. Chem. 2014, 79, 10605.
Zhang, N.; Yang, D.; Wei, W.; Yuan, Li.; Caob, Y.; Wang, H.
RSC Adv. 2015, 5, 37013.
Yotphan, S.; Sumunnee, L.; Beukeaw, D.; Buathongjan, C.;
Reutrakul, V. Org. Biomol. Chem. 2016, 14, 590; (b) Pan, X.;
Gao, J.; Liu, J.; Lai, J.; Jiang, H.; Yuan, G. Green Chem. 2015,
3
2
o
4.
5.
7
0 C, 10-12 h
I
OAc
O
S
H O
2
OAc O
S
O
O
S
I
R
R1
R2
1
R2
R1
R2
O
1
7, 1400.
Gao, J.; Pan, X.; Liu, J.; Lai, J.; Chang, L; Yuan, G. RSC Adv.
015, 5, 27439.
O
6
O
7
3
AcOH + HI
6.
7.
2
Scheme 2. A plausible mechanism for the formation of β-keto
sulfones.
Gao, J.; Lai, J.; Yuan, G. RSC Adv. 2015, 5, 66723.
Markitanov, Y. M.; Timoshenko, V. M.; Shermolovich, Y. G. J.
Sulfur Chem. 2014, 35, 188.
Yang, H.; Carter, R. G.; Zakharov, L. N. J. Am. Chem. Soc.
2
8
9
1
1
.
.
008, 130, 9238.
In summary, we have developed a novel protocol for direct
one-pot synthesis of β-keto sulfones using readily available,
stable and diversified arylenol acetates as substrates, sodium
sulfinates as sulfonaylating agents and iodine as an oxidizing
reagent. The present base-free and transition metal-free efficient
protocol offers a superior alternative and eco-compatible
approach to β-keto sulfones.
0. Kumar, A.; Muthyala, M. K.; Tetrahedron Lett. 2011, 52, 5368
and references cited therein.
1. (a) Xiang, J.; Ipek, M.; Suri, V.; Tam, M.; Xing, Y.-Z.; Huang,
N.; Zhang, Y.-L.; Tobin, J.; Mansoura, T. S. ; McKewa, J.;
Bioorg. Med. Chem. 2007, 15, 4396; (b) Xie, Y.; Chen, Z.-C.
Synth. Commun. 2001, 31, 3145; (c) Vennstra, Y.-G. E.;
Zwaneburg, B.; Synthesis 1975, 519.
1
2. Katritzky, A. R.; Abdel-Fattah, A. A.; Wang, M. Y. J. Org.
Chem. 2003, 68, 1443 and references cited therein.
Acknowledgments
13. (a) Zweifel, T.; Nielsen, M.; Overgaard, J.; Jacobsen, C. B.;
Jørgensen, K. A. Eur. J. Org. Chem. 2011, 47; (b) Loghmani-
Khouzani, H. H.; Poorheravi, M. P.; Sadeghi, M. M. M.;
Caggiano, L., Jackson, R. F. W. Tetrahedron 2008, 64, 7419; (c)
Trost, B. M.; Curran, D. P. Tetrahedron Lett. 1981, 22, 1287.
We sincerely thank SAIF, Punjab University, Chandigarh, for
providing microanalyses and spectra. V.K.Y. is grateful to the
CSIR, New Delhi, for the award of a Junior Research Fellowship
1
4. (a) Wai, W.; Wen, J.; Yang, D.; Guo, M.; Wang, Y.; You, J.
Wang, H. Org. Biomol. Chem. 2015, 13, 7084; (b) Handa, S.;
Fennewald, J. C.; Lipshutz, B. H. Angew. Chem. Int. Ed. 2014,
(Ref. No: 22/06/2014 (i) EU-V). V.P.S. is grateful to the
Department of Science and Technology (DST) Govt. of India, for
the award of a DST-Inspire Faculty position (Ref. IFA-11CH-08)
and financial support.
5
3, 3432; (c) Singh, A. K.; Chawla, R.; Yadav, L. D. S.
Tetrahedron Lett. 2014, 55, 2845; (d) Shi, X.-K.; Ren, X.-Y.;
Ren, Z.-Y.; Li, J.; Wang, Y.-L.; Yang, S.-Z.; Gu, J.-X.; Gao, Q.;
Huang, G.-S. Eur. J. Org. Chem. 2014, 5083; (e) Jiang, Y.-J.,
Loh, T.-P. Chem. Sci. 2014, 5, 4939; (f) Lu, Q.-Q.; Zhang, J.;
Zhao, G.-L., Qi, Y.; Wang, H.-M.; Lei, A.-W. J. Am. Chem. Soc.
References and notes
2
013, 135, 11481; (g) Wei, W.; Liu, C.-L.; Yang, D.-S.; Wen, J.-
W.; You, J.-M.; Suo, Y.-R.; Wang, H. Chem. Commun. 2013, 49,
0239.
5. (a) Hering, T.; Hari, D. P.; König, B. J. Org. Chem. 2012, 77,
0347 (b) Jiang, H.; Cheng, Y.; Zhang, Y.; Yu, S. Eur. J. Org.
1
.
(a) Zhu, T.H.; Wang, S. Y.; Tao, Y. Q.; Ji, S.J. Org. Lett. 2015,
7, 1974; (b) Tang, S.; Liu, K.; Long, Y.; Gao, X.; Gao, M.; Lei,
1
1
A. Org. Lett. 2015, 17, 2404; (c) Gao, Q.; Wu, X.; Liu, S.; Wu,
A. Org. Lett. 2014, 16, 1732; (d) Gao, Q.; Wu, X.; Li, Y.; Liu,
S.; Meng, X.; Wu, A. Adv. Synth. Catal. 2014, 356, 2924; (e)
Katrun, P.; Mueangkaew, C.; Pohmakotr, M.; Reutrakul, V.;
Jaipetch, T.; Soorukram, D.; Kuhakarn, C. J. Org. Chem. 2014,
1
1
1
Chem. 2013, 5485; (c) Lu, Y.; Li, Y.; Zhang, R.; Jin, K.; Duan,
C. J. Ful. Chem. 2014, 161, 128; (d) Tang, Y.; Fan, Y.; Gao, H.;
Li, X.; Xu, X. Tetrahedron Lett. 2015, 56, 5616.
7
4
7
9, 1778; (f) Ilangovan, A.; Satish, J. J. Org. Chem. 2014, 79,
984; (g) Ren, Y. M.; Cai, C.;Yang, R. C. RSC Adv. 2013, 3,
182; (h) Ge, W.; Zhu, X.; Wei, Y. Adv. Synth. Catal. 2013, 355,
6. Miura, K.; Fujisawa, N.; Saito, H.; Wang, D.; Hosomi, A. Org.
Lett. 2001, 3, 2591.