3
4a, 9, 12
Based on the above results and on previous reports,
a
Zhang, M.; Hu, M.; Cheng, J. J. Org. Chem. 2010, 75, 6732; (d)
Venkanna, G. T.; Arman, H. D.; Tonzetich, Z. J. ACS Catal. 2014,
, 2941; (e) Brachet, E.; Brion, J.-D.; Alami, M.; Messaoudi, S.
possible reaction pathway is proposed as shown in Scheme 3.
Initially, TBAI-assisted decomposition of TBHP generated the
tert-butoxyl radical, which abstracted hydrogen of sulfonyl
hydrazide to form sulfonyl radicals. Then, the addition of
resulting sulfonyl radicals to α-position of N,N-
dimethylenaminones 1 gave carbon radical (I). Futher oxidation
leads to the corresponding carbocation intermediate (II), which
4
Chem. Eur. J. 2013, 19, 15276; (f) Shen, T.; Yuan, Y.; Song, S. ;
Jiao, N. Chem. Commun. 2014, 50, 4115; (g) Wang, H.; Wang, L.;
Shang, J.; Li, X.; Wang, H.; Gui, J.; Lei, A. Chem. Commun.
2012, 48, 76; (h) Yang, L.; Wen, Q.; Xiao, F.; Deng, G. Org.
Biomol. Chem., 2014, 12, 9519; (i) Singh, A. K.; Chawla, R.;
Keshari, T.; Yadav, V. K.; Yadav, L. D. S. Org. Biomol. Chem.,
2
014,12, 8550.
following by the nucleophilic attack of H
2
O to give intermediate
III). Finally, the loss of a molecule of N, N-dimethylformamide
DMF) from intermediate (III) leading to β-ketosulfones.
4
.
(a) Li, X.; Xu, X.; Zhou, C. Chem.Commun. 2012, 48, 12240; (b)
Lu,Q.; Zhang, J.; Zhao,G.; Qi, Y.; Wang, H.; Lei, A. J. Am .Chem.
Soc. 2013, 135, 11481; (c) Wei, W.; Liu, C.; Yang, D.; Wen, J.;
You, J.; Suo, Y.; Wang, H. Chem.Commun. 2013, 49, 10239; (d)
Wei, W.; Wen, J.; Yang, D.; Wu, M.; You, J.; Wang, H. Org.
Biomol. Chem. 2014, 12, 7678; (e)Singh, A. K.; Chawla, R.;
Yadav, L. D. S. Tetrahedron Lett. 2014, 55, 4742; (f) Singh, A.
K.; Chawla, R.; Keshari, T.; Yadav,V. K.; Yadav, L. D. S. Org
.Biomol. Chem. 2014, 12, 8550; (g) Lu, Q.; Wang, H.; Peng, P.;
Liu, C.; Huang, Z.; Luo, Y. ; Lei, A. Org. Chem. Front. 2015, 2,
(
(
OH
H2O
+
t-BuOO
t-BuOOH
/2 I2
1
I
t-BuOOH
t-BuO
+
OH
9
08; (h) Wang, H.; Wang, G.; Lu, Q.; Chiang, C.-W.; Peng, P.;
O
Zhou, J.; Lei, A. Chem. Eur. J. 2016, 22, 14489; (i) Yang, D.;
Huang B.; Wei, W.; Li, J.; Lin, G.; Liu, Y.; Ding, J.; Sun, P.;
Wang, H. Green Chem. 2016, 18, 5630; (j) Wang, H.; Lu, Q.;
Qian, C.; Liu, C.; Liu, W.; Chen, K.; Lei, A. Angew. Chem. Int.
Ed. 2016, 55, 1094.
t-BuOOH
or
t-BuOH
CH3
t-BuOO
or t-BuO
N
O
O
CH3
O
S
S
SO2NHNH2
O
CH3
O
N
N2
CH3 (I)
5
6
.
.
(a) Curti, C.; Laget, M.; Carle, A. O.; Gellis, A.; Vanelle, P. Eur.
J. Med. Chem. 2007, 42, 880; (b) Yang, H.; Carter, R. G.;
Zakharov, L. N. J. Am. Chem. Soc. 2008, 130, 9238; (c) Kumar,
A.; Muthyala, M. K. Tetrahedron Lett. 2011, 22,1287.
[
O ]
(a) Vennstra, G. E.; Zwaneburg, B. Synthesis, 1975, 519; (b) Xie,
Y.-Y.; Chen, Z.-C. Synth. Commun., 2001, 31, 3145; (c) Kumar,
D.; Sundaree, S.; Rao, V.S.; Varma, R. S. Tetrahedron Lett. 2006,
47, 4197; (d) Bouhlel, A.; Curti, C. ;Tabelé, C.; Vanelle, P.
Molecules 2013, 18, 4293; (e) Rawat, V. S.; Reddy P. L.
M.; Sreedhar B. RSC Adv. 2014, 4, 5165.
O
O
O
O
O
O
S
S
S
H2O
-
DMF
O
O
O
CH3
N
(II)
CH3
HO
N
CH3
CH3
(III)
7
8
.
.
Xiong, Y.; Weng, J.; Lu, G. Adv. Synth.Catal. 2018, 360, 1611.
Tang, X.; Huang, L.; Xu, Y.; Yang, J.; Wu, W.; Jiang, H. Angew.
Chem. Int. Ed. 2014, 53, 4205.
Scheme 3. Proposed preliminary mechanisms
9
.
(a) Tang,Y.; Zhang, Y. ; Wang, K.; Li, X.; Xu, X.; Du. X. Org.
Biomol. Chem. 2015, 13, 7084; (b) Tang, Y.; Fan, Y.; Gao, H.; Li,
X.; Xu. X. Tetrahedron Lett. 2015, 56, 5616.
In conclusion, we have reported a novel TBAI-catalyzed
radical sulfonylation of readily available N,N-
dimethylenaminones with sulfonylhydrazides to afford
10. (a) Lan, X.; Wang,N.; Bai,C.; Zhang, W.; Xing, Y. Wen, J.;
Wang, Y.; Li, Y. Scientific Report. 2015, 5, 18391; (b) Wang, Y.;
Ma, L.; Ma, M.; Zheng, H.; Shao, Y.; Wan, X. Org. Lett. 2016,
13
functionalized β-keto-sulfones. Various functional groups were
tolerated well under the present oxidative conditions and the
corresponding β-keto-sulfone compounds were obtained in
moderate to good yields. Importantly, this transformation offered
1
1. A possible explanation of dehalogenation process by the
8, 5082.
1
nucleophilic alkyl radical, see: Hokamp, T.; Dewanji, A.;
Lgbbesmeyer, M.; Mgck-Lichtenfeld, C.; Wgrthwein, E.; Studer,
A. Angew. Chem. Int. Ed. 2017, 56, 13275.
3
2
the first protocol for Csp -S bond formation by oxidative Csp -
2
Csp bond cleavage in one step. Further studies on the scope and
application of this reaction are under way in our laboratory.
1
2. (a) Wei, W.; Wen, J.; Yang, D.; Guo, M.; Wang, Y.; You, J.;
Wang, H. Chem. Commun., 2015, 51, 768; (b) Zhang, J.; Shao, Y.;
Wang, H.; Luo, Q.; Chen, J.; Xu, D.; Wan, X. Org.
Lett., 2014, 16 , 3312; (c) Zhou, P.; Hu, B.; Li, L.; Rao, K.; Yang,
J.; Yu, F. J. Org. Chem. 2017, 82, 13268; (d) Wan, J.; Zhong, S.;
Guo, Y.; Wei, L., Eur. J. Org. Chem. 2017, 4401.
Acknowledgments
This project is supported by the Start-up Foundation for
Doctors of Hunan University of Arts and Science (17BSQD32),
and Ministry of Education and the Construct Program of the Key
Discipline in Hunan Province (Applied Chemistry).
1
3. Typical Procedure for the Synthesis of 3
To a stirred solution of N,N-dimethylenaminone (0.25 mmol),
2
TsNHNH (0.5 mmol) and TBAI (0.05 mmol) in 1,4-dioxane (2
mL) was added TBHP (0.5 mmol, 70% aqueous solution) at room
o
temperature. The mixture was heated at 80 C for 8 h and cooled
down to room temperature. The excess solvent was removed under
vacuum, and the residue was directly purified by silica gel column
References and notes
chromatography to afford desired β-keto-sulfones.
1
2
3
.
.
.
For selected examples, see: (a) Napier, C.; Stewart, M.; Melrose,
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-phenyl-2-tosylethanone(3a). H NMR (500 MHz, CDCl
1
(
3
) δ 7.95
d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.66-7.58 (m, 1H),
3
75, 61;(b) Petrov, K. G.; Zhang, Y.; Carter, M.; Cockerill, G.
7
2
1
.48 (t, J = 7.8 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H), 4.72 (s, 2H),
) δ 188.1, 145.4, 135.8,
35.8, 134.3, 129.8, 129.3, 128.8, 128.6, 63.6, 21.7.
S.;Dickerson, S.; Gauthier, C. A.; Guo, Y.; Mook, R. A.; Rusnak,
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13
.44 (s, 3H). C NMR (125 MHz, CDCl
3
(a) Nakazawa, T.; Xu, J.; Nishikawa, T.; Oda, T.; Fujita, A.; Ukai,
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For selected examples, see: (a) Zhang, X.; Zeng, W.; Yang, Y.;
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Jiang, X. Org. Lett. 2014, 16, 2692; (c) Zhang, S.; Qian, P.;
Supplementary Material
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