Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
Z. He, B. Gao, L. Li, C. Ni, J. Hu, J. Am.DCOhIe: m10..1S0o3V9ci/.e,Cw29AC0rt1Cic30le,5O21n93l3in5Ce,
17302. (e) Y. Huang, T. Hayashi, J. Am. Chem. Soc., 2016, 138,
12340. (f) K. Fuchibe, H. Hatta, K. Oh, R. Oki, J. Ichikawa,
Angew. Chem. Int. Ed., 2017, 56, 5890.
(a) C. Schneider, D. Masi, S. Couve-Bonnaire, X.
Pannecoucke, C. Hoarau, Angew. Chem. Int. Ed., 2013, 52,
3246. (b) K. Rousée, C. Schneider, S. Couve-Bonnaire, X.
Pannecoucke, V. Levacher, C. Hoarau, Chem. Eur. J., 2014,
20, 15000.
(a) P. Tian, C. Feng, T. -P. Loh, Nat. Commun., 2015, 6, 7472.
(b) D. Zell, U. Dhawa, V. Müller, M. Bursch, S. Grimme, L.
Ackermann, ACS Catal., 2017, 7, 4209. (c) J. -Q. Wu, S. -S.
Zhang, H. Gao, Z. Qi, C. -J. Zhou, W. -W. Ji, Y. Liu, Y. Chen, Q.
Li, X. Li, H. Wang, J. Am. Chem. Soc., 2017, 139, 3537.
(a)X. -W. Liu, J. Echavarren, C. Zarate, R. Martin, J. Am. Chem.
Soc., 2015, 137, 12470. (b) T. Niwa, H. Ochiai, Y. Watanabe,
T. Hosoya, J. Am. Chem. Soc., 2015, 137, 14313. (c) A. M.
Mfuh, J. D. Doyle, B. Chhetri, H. D. Arman, O. V. Larionov, J.
Am. Chem.Soc., 2016, 138, 2985. (d) J. Zhou, M. W. Kuntze-
Fechner, R. Bertermann, U. S. D. Paul, J. H. J. Berthel, A.
Friedrich, Z. Du, T. B. Marder, U. Radius, J. Am. Chem. Soc.,
2016, 138, 5250. (e) T. Niwa, H. Ochiai, T. Hosoya, ACS Catal.,
2017, 7, 4535.
comitant regeneration of the ground-state photocatalyst
Finally, the elimination process of occured after the extrusion
of a F- of the intermediate C , provides the desired product 3a.
light
5
6
7
Ir
3a
Ir
- F
F
PMPS
Base
PMP-SH
R-S
SET
F
2a
SET
C
Ir
R-S
A
F
F
PMPS
F
R-S
A
F
B
1a
Scheme 3.Proposed reaction mechanism.
8
9
T. Hanamoto, S. Harada, K. Shindo, M. Kondo, Chem.
Commun., 1999, 2397.
(a) H. Sakaguchi, M. Ohashi, S. Ogoshi, Angew. Chem. Int.
Ed., 2018, 57, 328. (b) H. Sakaguchi, Y. Uetake, M. Ohashi, T.
Niwa, S. Ogoshi, T. Hosoya, J. Am. Chem. Soc., 2017, 139,
12855.
In conclusion, we have discovered an efficient and mild
protocol for the defluorinative cross-coupling of thiols
withgem-difluoroalkenes.
A variety of thiols and gem-
difluoroalkenes could undergo this reaction to selectively
provide C-S coupling products in moderate to excellent yield.
Furthermore, the synthetic potential has been demonstrated
by a gram-scale synthesis and late-stage functionalization of
natural products. Further exploration will be focused on C-F
activation processes.
The authors gratefully acknowledge for the financial support
from the National Natural Science Foundation of China (Grant
No. 21672047), SKLUWRE (No. 2018DX02) and The Science and
Technology Plan of Shenzhen (JCYJ20180306172044124).
10 (a) X. Lu, Y. Wang, B. Zhang, J. -J. Pi, X. -X. Wang, T. -J. Gong,
B. Xiao, Y. Fu, J. Am. Chem. Soc., 2017, 139, 12632. (b) L.
Zhou, C. Zhu, P. Bi, C. Feng, Chem. Sci., 2019,10, 1144.
11 (a) M. Feng, B. Tang, S. Liang, X. Jiang, Curr. Top. Med. Chem.,
2016, 16, 1200. (b) E. A. Ilardi, E. Vitaku, J. T. Njardarson, J.
Med. Chem., 2014, 57, 2832. (c) D. A. Boyd, Angew. Chem.,
Int. Ed., 2016, 55, 15486.
12 (a) F. Dénès, M. Pichowicz, G. Povie, P. Renaud, Chem. Rev.,
2014, 114, 2587. (b) E. D. Goddard-Borger, M. B. Tropak, S.
Yonekawa, C. Tysoe, D. J. Mahuran, S. G. Withers, J. Med.
Chem., 2012, 55, 2737. (c) E. P. Kohler, H. Potter, J. Am.
Chem. Soc., 1935, 57, 1316. (d) L. I. Smith, H. R. Davis, J. Org.
Chem. 1950, 15, 824. (e) J. Jin, D. W. C. MacMillan, Nature
2015, 525, 87. (f) D. Hager, D. W.C. MacMillan, J. Am. Chem.
Soc., 2014, 136, 16986. (g) A. G. Capacci, J. T. Malinowsk, N.
J. McAlpine, J. Kuhne, D. W. C. MacMillan, Nat. Chem., 2017,
9, 1073. (h) M. Teders, C. Henkel, L. Anhäuser, F. Strieth-
Kalthoff, A. Gómez-Suárez, R. Kleinmans, A. Kahnt, A.
Rentmeister, D. Guldi, F. Gloriusꢀ, Nat. Chem., 2018, 10, 981.
13 (a) J. F. Hartwig, Acc. Chem. Res., 2008, 41, 1534. (b) C.
Uyeda, Y. Tan, G. C. Fu, J. C. Peters, J. Am. Chem. Soc., 2013,
135, 9548.
14 (a) X. Wang, G. D. Cuny, T. Noël, T. Angew. Chem. Int. Ed.,
2013, 52, 7860. (b) M. S. Oderinde, M. Frenette, D. W.
Robbins, B. Aquila, J. W. Johannes, J. Am. Chem. Soc., 2016,
138, 1760. (c) M. Jouffroy, C. B. Kelly, G. A. Molander, Org.
Lett., 2016, 18, 876.
15 J. F. Bunnett, X. Creary, J. Org. Chem., 1974, 39, 3173.
16 (a) J. Xie, J. Yu, M. Rudolph, F. Rominger, A. S. K. Hashmi,
Angew. Chem. Int. Ed., 2016, 55, 9416. (b) J. Xie, M. Rudolph,
F. Rominger, A. S. K. Hashmi, Angew. Chem. Int. Ed., 2017,
56, 7266. (c) J. Li, Q. Lefebvre, H. Yang, Y. Zhao, H. Fu, Chem.
Commun., 2017, 53, 10299. (d) J. Xie, H. Jin, A. S. K. Hashmi,
Chem. Soc. Rev., 2017, 46, 7475193. (e) J. Xie, J. Yu, M.
Rudolph, F. Rominger, A. S. K. Hashmi, Angew. Chem. Int.
Ed., 2016, 55, 9416(f) Z. Cong, Y. Li, L, Chen, F. Xing, G. Du, C.
Gu, H. He. Org. Biomol. Chem.2017, 15, 3863.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
2
(a) W. K. Hagmann, J. Med. Chem., 2008, 51, 4359. (b) P.
Kirsch,
Modern Fluoroorganic Chemistry: Synthesis,
Reactivity, Applications. (Wiley, 2004).
(a) S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem.
Soc. Rev., 2008, 37, 320. (b) K. Müller, C. Faeh, F. Diederich,
Science 2007, 317, 1881. (c) P. Jeschke, ChemBioChem. 2004,
5, 570. (d) T. Liang, C. N. Neumann, T. Ritter, Angew. Chem.
Int. Ed., 2013, 52, 8214. (e) T. Furuya, A. S. Kamlet, T. Ritter,
Nature 2011, 473, 470.
3
4
(a) J. Lin, P. J. Toscano, J. T. Welch, Proc. Natl. Acad. Sci. U. S.
A., 1998, 95, 14020. (b) G. Dutheuil, S. Couve-Bonnaire, X.
Pannecoucke, Angew. Chem. Int. Ed., 2007, 46, 1290. (c) G.
Landelle, M. Bergeron, M. -O. Turcotte-Savard, J. -F. Paquin,
Chem. Soc. Rev., 2011, 40, 2867. (d) O. E. Okoromoba, J. Han,
G. B. Hammond, B. Xu, J. Am. Chem. Soc., 2014, 136, 14381.
(e) Y. Zhao, F. Jiang, J. Hu, J. Am. Chem. Soc., 2015, 137,
5199. (f) T. -L. Liu, J. E. Wu, Y. Zhao, Chem. Sci., 2017, 8,
3885.
(a) M. Takachi, Y. Kita, M. Tobisu, Y. Fukumoto, N. Chatani,
Angew. Chem. Int. Ed., 2010, 49, 8717. (b) M. Ohashi, T.
Kambara, T. Hatanaka, H. Saijo, R. Doi, S. Ogoshi, J. Am.
Chem. Soc., 2011, 133, 3256. (c) J. Zheng, J. Cai, J. -H. Lin, Y.
.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins