Page 3 of 4
ChemComm
Please do not adjust margins
Journal Name COMMUNICATION
3
Pharmaceutical Substance: SynthesisDPOaI:t1e0n.1t0s3, V9Ai/eDwp0pACrltiCicc0ale1tO3io8nnl0insCe,
4th ed., Georg Thieme, Stuttgart, 2001; (b) F. F. Fleming and Q.
Wang, Chem. Rev., 2003, 103, 2035.
(a) P. Anbarasan, T. Schareina and M. Beller, Chem. Soc. Rev.,
2011, 40, 5049; (b) Q. Wen, J. Jin, L. Zhang, Y. Luo, P. Lu, Y.
Wang, Tetrahedron Lett., 2014, 55, 1271.
(a) J. Kim, H. J. Kim and S. Chang, Angew. Chem. Int. Ed., 2012,
51, 11948; Angew. Chem., 2012, 124, 12114; (b) X. Fang, P. Yu
and B. Morandi, Science 2016, 351, 832; (c) J. Schorgenhumer
and M. Waser, Org. Chem. Front., 2016, 3, 1535; (d) G. Yan, Y.
Zhang and J. Wang Adv. Synth. Catal., 2017, 359, 4068; (e) F.
Le Vaillant, M. D. Wodrich and J. Waser, Chem. Sci., 2017, 8,
1790; (f) P. Yu and B. Morandi, Angew. Chem. Int. Ed., 2017,
56, 15693; (g) A. W. Schuppe, G. M. Borrajo-Calleja and S. L.
Buchwald, J. Am. Chem. Soc., 2019, 141, 18668; (h) H. Chen, A.
Mondal, P. Wedi and M. van Gemmeren, ACS Catal., 2019, 9,
1979; (i) D. Zhao, P. Xu and T. Ritter, Chem, 2019, 5, 97; (j) J.
Long, J. Gao and X. Fang, Org. Lett., 2020, 22, 376; (k) H. Chen,
S. Sun, Y. A. Liu and X. Liao, ACS Catal., 2020, 10, 1397; (l) Y.
Xing, R. Yu and X. Fang, Org. Lett., 2020, 22, 1008.
deprotonation/elimination in the presence of base produces
the desired final nitrile product 2.
In summary, a visible light mediated dehydrosulfurization of
thioamides to nitriles has been demonstrated for the first time.
This new approach features the high reaction yield, good
functional-group tolerance, and the use of a cheap organic dye
(Methylene Blue) as the photocatalyst and air as the
environmentally benign oxidant.
4
5
S
S
- H
base
R
NH2
R
NH
3
4
S
SET
MB
R
NH2
O2
1
SET
O2
MB*
SOO
N
6
7
(a) T. S. Jagodzinski, Chem. Rev., 2003, 103, 197; (b) D. P. N.
Satchell, Chem. Soc. Rev., 1977, 6, 345.
- H
R
CN
2-
visible light
R
- SO2
MB
2
5
H
(a) M. Lim, W. Y. Ren and R. S. Klein, J. Org. Chem., 1982, 47,
4594; (b) H. Suzuki, H. Tani and S. Takeuchi, Bull. Chem. Soc.
Jpn., 1985, 58, 2421; (c) D. S. Bose, B. Jayalakshmi and P. R.
Goud, Synthesis, 1999, 1724; (d) M. Avalos, R. Babiano, P.
Cintas, C. J. Durán, F. J. Higes, J. L. Jiménez, I. López and J. C.
Palacios, Tetrahedron, 1997, 53, 14463; (e) T. Mineno, Y.
Takebe, C. Tanaka and S. Mashimo, Int. J. Org. Chem., 2014, 4,
169
K. Yamaguchi, K. Yajima and N. Mizuno, Chem. Commun.,
2012, 48, 11247.
E. Gopi, V. Geertsen, E. Gravel and E. Doris, ChemCatChem
2019, 11, 5758.
Scheme 2 Proposed mechanism
Financial support provided by the Natural Science Foundation
of China (No. 21602028), the Recruitment Program of Global
Experts, Natural Science Foundation of the Jiangsu Higher
Education Institutions of China (17KJA220003), and Fuzhou
University is acknowledged.
8
9
Conflicts of interest
10 For reviews, see: (a) J. M. R. Narayanam and C. R. J.
Stephenson, Chem. Soc. Rev., 2011, 40, 102; (b) J. Xuan and
W.-J. Xiao, Angew. Chem. Int. Ed., 2012, 51, 6828; (c) T. P.
Yoon, M. A. Ischay and J. N. Du, Nat. Chem., 2010, 2, 527; (d)
K. Zeitler, Angew. Chem. Int. Ed., 2009, 48, 9785.
11 For visible light-mediated synthesis of nitriles, see: (a) J. B.
McManus and D. A. Nicewicz, J. Am. Chem. Soc., 2017, 139,
2880; (b) F. L. Vaillant, M. D. Wodrich and J. Waser, Chem. Sci.,
2017, 8, 1790; (c) D. Wang, N. Zhu, P. Chen, Z. Lin, G. Liu, J. Am.
Chem. Soc., 2017, 139, 15632; (d) Y.-L. Ban, J.-L. Dai, X.-L. Jin,
Q.-B. Zhang and Q. Liu, Chem. Commun., 2019, 55, 9701; (e) N.
P. Ramirez, B. König and J. C. Gonzalez-Gomez, Org. Lett. 2019,
21, 1368; (f) Y.-H. Li, P. S. Akula, B.-C. Hong, C.-H. Peng and G.-
H. Lee, Org. Lett., 2019, 21, 7750; (g) W. Liu, J. Li, P. Querard
and C.-J. Li, J. Am. Chem. Soc., 2019, 141, 6755;
There are no conflicts to declare
Notes and references
1
(a) D. Enders and J. P. Shilvock, Chem. Soc. Rev., 2000, 29, 359;
(b) N. Otto and T. Opatz, Chem. Eur. J., 2014, 20, 13064; (c) D.
B. Bagala and B. M. Bhanage, Adv. Synth. Catal., 2015, 357,
883; (d) M.-X. Wang, Acc. Chem. Res., 2015, 48, 602.
(a) F. F. Fleming, Nat. Prod. Rep., 1999, 16, 597; (b) R. J. H.
Gregory, Chem. Rev., 1999, 99, 3649; (c) J. S. Miller and J. L.
Manson, Acc. Chem. Res., 2001, 34, 563; (d) F. F. Fleming, L. H.
Yao, P. C. Ravikumar, L. Funk and B. C. Shook, J. Med. Chem.,
2010, 53, 7902; (e) P. Hu, J. C. Chai, Y. L. Duan, Z. H. Liu, G. L.
Cui and L. Q. Chen, J. Mater. Chem. A, 2016, 4, 10070.
2
12 S. H. Chang, G. H. Yon, and Y. H. Kim, Chem. Lett., 1986, 1291.
13 J.-G. Sun, H. Yang, P. Li and B. Zhang, Org. Lett., 2016, 18, 5114.
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins