Sulfoximines as S-Aryl Surrogates: A Photocatalytic Rapid, Metal-Free, Mild Protocol to Access 3-Arylsulfenyl Indoles

Abstract

Sulfoximines as S-aryl surrogates permit the preparation of 3-arylsulfenylindoles through reaction with indoles in the presence of I₂ under visible-light irradiation. This environmentally friendly approach is fast, mild, metal-, photocatalyst-, additive-, and oxidant-free, and it provides the desired products in moderate to good yields with a wide substrate scope.

Key words

sulfoximines - S-aryl surrogates - arylsulfenylindoles - green chemistry - metal-free reaction

Publication History

Received: 18 April 2023

Accepted after revision: 07 June 2023

Accepted Manuscript online:
07 June 2023

Article published online:
31 July 2023

• References and Notes

• 1a Lücking U. Angew. Chem. Int. Ed. 2013; 52: 9399
• 1b Andresini M, Tota A, Degennaro L, Bull JA, Luisi R. Chem. Eur. J. 2021; 27: 17293
• 2 Mäder P, Kattner L. J. Med. Chem. 2020; 63: 14243
• 3 Han Y, Xing K, Zhang J, Tong T, Shi Y, Cao H, Yu H, Zhang Y, Liu D, Zhao L. Eur. J. Med. Chem. 2021; 209: 112885
• 4 Bull JA, Degennaro L, Luisi R. Synlett 2017; 28: 2525
• 5 Ghosh P, Ganguly B, Das S. Asian J. Org. Chem. 2020; 9: 2035
• 6 Li Z, Yu H, Bolm C. Angew. Chem. Int. Ed. 2017; 56: 9532
• 7a Thanikachalam PV, Maurya RK, Garg V, Monga V. Eur. J. Med. Chem. 2019; 180: 562
• 7b Taber DF, Tirunahari PK. Tetrahedron 2011; 67: 7195
• 7c Zhang M.-Z, Chen Q, Yang G.-F. Eur. J. Med. Chem. 2015; 89: 421
• 8a Choudhury P, Roy B, Basu B. Asian J. Org. Chem. 2017; 6: 1569
• 8b Yi S, Li M, Mo W, Hu X, Hu B, Sun N, Jin L, Shen Z. Tetrahedron Lett. 2016; 57: 1912
• 8c Li W, Wang H, Liu S, Feng H, Benassi E, Qian B. Adv. Synth. Catal. 2020; 362: 2666
• 9 Mitamura T, Iwata K, Ogawa A. J. Org. Chem. 2011; 76: 3880
• 10 Han D, Li Z, Fan R. Org. Lett. 2014; 16: 6508
• 11 Chitra S, Paul N, Muthusubramanian S, Manisankar P. RSC Adv. 2012; 2: 1432
• 12 Liu J, Li P, Chen W, Wang L. Chem. Commun. 2012; 48: 10052
• 13 Yadav JS, Reddy BV. S, Reddy YJ, Praneeth K. Synthesis 2009; 1520
• 14 Maeda Y, Koyabu M, Nishimura T, Uemura S. J. Org. Chem. 2004; 69: 7688
• 15a Schlosser KM, Krasutsky AP, Hamilton HW, Reed JE, Sexton K. Org. Lett. 2004; 6: 819
• 15b Yadav JS, Reddy BV. S, Reddy YJ. Tetrahedron Lett. 2007; 48: 7034
• 15c Liu Y, Zhang Y, Hu C, Wan J.-P, Wen C. RSC Adv. 2014; 4: 35528
• 15d Sorabad GS, Maddani MR. Asian J. Org. Chem. 2019; 8: 1336
• 15e Guo W, Tan W, Zhao M, Tao K, Zheng L.-Y, Wu Y, Chen D, Fan X.-L. RSC Adv. 2017; 7: 37739
• 16 Zhang H, Bao X, Song Y, Qu J, Wang B. Tetrahedron 2015; 71: 8885
• 17 Han D.-Y, Liu X.-P, Li R.-P, Xu D.-Z. J. Org. Chem. 2021; 86: 10166
• 18 Ge W, Wei Y. Synthesis 2012; 44: 934
• 19a Azeredo JB, Godoi M, Martins GM, Silveira CC, Braga AL. J. Org. Chem. 2014; 79: 4125
• 19b Huang D, Chen J, Dan W, Ding J, Liu M, Wu H. Adv. Synth. Catal. 2012; 354: 2123
• 19c Sang P, Chen Z, Zou J, Zhang Y. Green Chem. 2013; 15: 2096
• 20 Li Z, Hong J, Zhou X. Tetrahedron 2011; 67: 3690
• 21 Ge W, Wei Y. Green Chem. 2012; 14: 2066
• 22 Zhou X, Li X. RSC Adv. 2014; 4: 1241
• 23 Fang X.-L, Tang R.-Y, Zhong P, Li J.-H. Synthesis 2009; 4183
• 24a Chen M, Huang Z.-T, Zheng Q.-Y. Chem. Commun. 2012; 48: 11686
• 24b He Y, Jiang J, Bao W, Deng W, Xiang J. Tetrahedron Lett. 2017; 58: 4583
• 25 Kumaraswamy G, Raju R, Narayanarao V. RSC Adv. 2015; 5: 22718
• 26 Rao H, Wang P, Wang J, Li Z, Sun X, Cao S. RSC Adv. 2014; 4: 49165
• 27 Xiao F, Xie H, Liu S, Deng G.-J. Adv. Synth. Catal. 2014; 356: 364
• 28 Liu C.-R, Ding L.-H. Org. Biomol. Chem. 2015; 13: 2251
• 29 Rahaman R, Devi N, Bhagawati JR, Barman P. RSC Adv. 2016; 6: 18929
• 30 Yang F.-L, Tian S.-K. Angew. Chem. Int. Ed. 2013; 52: 4929
• 31 Wang F.-X, Zhou S.-D, Wang C, Tian S.-K. Org. Biomol. Chem. 2017; 15: 5284
• 32a Hamel P, Préville P. J. Org. Chem. 1996; 61: 1573
• 32b Raban M, Chern L.-J. J. Org. Chem. 1980; 45: 1688
• 33 Tudge M, Tamiya M, Savarin C, Humphrey GR. Org. Lett. 2006; 8: 565
• 34 Marcantoni E, Cipolletti R, Marsili L, Menichetti S, Properzi R, Viglianisi C. Eur. J. Org. Chem. 2013; 2013: 132
• 35 Guo Y.-J, Tang R.-Y, Li J.-H, Zhong P, Zhang X.-G. Adv. Synth. Catal. 2009; 351: 2615
• 36a Narayanam JM. R, Stephenson CR. J. Chem. Soc. Rev. 2011; 40: 102
• 36b Prier CK, Rankic DA, MacMillan DW. C. Chem. Rev. 2013; 113: 5322
• 36c Romero NA, Nicewicz DA. Chem. Rev. 2016; 116: 10075
• 36d Priya VR. P, Natarajan K, Nandi GC. Tetrahedron 2022; 111: 132711
• 37 Kumar A, Gupta G, Srivastava S. Org. Lett. 2011; 13: 6366
• 38 Wei Y, Chu H, Tian Y, Chen B, Wu K, Wang J, Yang X, Cai B, Zhang Y, Zhao J. Adv. Energy Mater. 2019; 9: 1900612
• 39 3-[(4-Chlorophenyl)sulfanyl]-1H-indole (3aa); Typical Procedure A clean 20 mL Schlenk tube was charged with sulfoximine 1a (32 mg, 0.1687 mmol, 1.0 equiv), indole (2a; 20 mg, 0.1707 mmol, 1.0 equiv), and I₂ (43 mg, 0.1694 mmol, 1.0 equiv) in EtOH (1 mL). The mixture was stirred at RT under blue LED irradiation (456 nm/50 W) for 10 mins. When the reaction was complete (TLC; reaction time 10–15 min, depending on the substrate), the solvent was removed in vacuo and the product was purified by column chromatography [silica gel (100–200 mesh), 2–10% EtOAc–hexane] to give a white solid; yield: 36 mg (81%); mp 130–131 °C. ¹H NMR (500 MHz, CDCl₃): δ = 8.38 (br s, 1 H), 7.56 (d, J = 8.0 Hz, 1 H), 7.45 (d, J = 3.0 Hz, 1 H), 7.42 (d, J = 8.0 Hz, 1 H), 7.28–7.23 (m, 1 H), 7.16 (td, J = 8.0, 1.0 Hz, 1 H), 7.11–7.08 (m, 2 H), 7.02–6.99 (m, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = 137.9, 136.6, 130.8, 130.6, 128.9, 128.8, 127.2, 123.3, 121.2, 119.6, 111.8, 102.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₄H₁₁ClNS: 260.0295; found: 260.0294.