N-Fluorobenzenesulfonimide-Mediated Oxidative Rearrangement of Tetrahydro-β-carbolines

Abstract

Oxidative rearrangement of tetrahydro-β-carbolines is recognized as a biosynthetic process and represents one of the most popular and efficient approaches for the synthesis of spiro[pyrrolidine-3,3]oxindoles, which belong to an important structural scaffold that widely exists in a wide spectrum of pharmaceutically active compounds and natural products. Although halogenated reagents including t-BuOCl, NBS, and NIS, have been frequently used as oxidants for this oxidative rearrangement, fluorinated reagents have not been successfully employed. Here, a universal and efficient oxidative rearrangement of tetrahydro-β-carbolines using N-fluorobenzenesulfonimide (NFSI) as the oxidant is reported, affording a variety of spiro[pyrrolidine-3,3]oxindoles in excellent yields (90–99%). Owing to the increased oxidative ability and hardness of fluorine over other halogens, this method would be instrumental to rapid access of structurally diverse spirooxindoles.

Key word

tetrahydro-β-carbolines - spirooxindoles - oxidative rearrangement - N–F reagent - synthetic method

Publikationsverlauf

Eingereicht: 11. Februar 2025

Angenommen nach Revision: 17. März 2025

Accepted Manuscript online:
17. März 2025

Artikel online veröffentlicht:
10. April 2025

• References

• 1a Ye N, Chen H, Wold EA, Shi P.-Y, Zhou J. ACS Infect. Dis. 2016; 2: 382
• 1b Santos MM. M. Tetrahedron 2014; 70: 9735
• 1c Zhou L.-M, Qu R.-Y, Yang G.-F. Expert Opin. Drug Discov. 2020; 15: 603
• 2a Marti C, Carreira EM. Eur. J. Org. Chem. 2003; 2209
• 2b Trost BM, Brennan MK. Synthesis 2009; 3003
• 2c Dalpozzo R, Bartoli G, Bencivenni G. Chem. Soc. Rev. 2012; 41: 7247
• 2d Cheng D, Ishihara Y, Tan B, Barbas CF. ACS Catal. 2014; 4: 743
• 2e Cao Z.-Y, Zhou F, Zhou J. Acc. Chem. Res. 2018; 51: 1443
• 3a Szabó LF. Molecules 2008; 13: 1875
• 3b O’Connor SE, Maresh JJ. Nat. Prod. Rep. 2006; 23: 532
• 3c Smith JM, Moreno J, Boal BW, Garg NK. Angew. Chem. Int. Ed. 2015; 54: 400
• 4a Imaoka S, Nakashima Y, Kitajima M, Ishikawa H. Chem. Pharm. Bull. 2024; 72: 68
• 4b Zhang Y, Zhang L, Qi X. Angew. Chem. Int. Ed. 2023; 62: e202304435
• 4c Stephen MR, Rahman MT, Tiruveedhula VP. B, Fonseca GO, Deschamps JR, Cook JM. Chem. Eur. J. 2017; 23: 15805
• 4d White JD, Li Y, Ihle DC. J. Org. Chem. 2010; 75: 3569
• 4e Hu J, Niu ZX, Wang JF. Molecules 2024; 29: 1655
• 5a Zinnes H, Shavel JJr. J. Org. Chem. 1966; 31: 1765
• 5b Peterson AC, Cook JM. Tetrahedron Lett. 1994; 35: 2651
• 5c Xu J, Liang L, Zhang H, Chi YR, Tong R. Nat. Commun. 2019; 10: 4754
• 5d Wang J, Chen Y, Du W, Chen N, Fu K, He Q, Shao L. Tetrahedron 2022; 127: 133101
• 6a Finch N, Taylor WI. J. Am. Chem. Soc. 1962; 84: 3871
• 6b Hinman RL, Bauman CP. J. Org. Chem. 1964; 29: 1206
• 6c Qian C, Li P, Sun J. Angew. Chem. Int. Ed. 2020; 60: 5871
• 6d Sathish M, Sakla AP, Nachtigall FM, Santos LS, Shankaraiah N. RSC Adv. 2021; 11: 16537
• 7a Zheng Y, Cheung YT, Liang L, Qiu H, Zhang L, Tsang A, Chen Q, Ton R. Chem. Sci. 2022; 13: 10479
• 7b Sato E, Kangawa S, Mitsudo K, Suga S. Chem. Lett. 2022; 51: 1067
• 7c Liu D, Xu H. Eur. J. Org. Chem. 2023; 26: e202200987
• 8a Richter JM, Ishihara Y, Masuda T, Whitefield BW, Llamas T, Pohjakallio A, Baran PS. J. Am. Chem. Soc. 2008; 130: 17938
• 8b Baran PS, Maimone TJ, Richter JM. Nature 2007; 446: 404
• 9a Takeuchi Y, Tarui T, Shibata N. Org. Lett. 2000; 2: 639
• 9b Jiang X, Yang J, Zhang F, Yu P, Yi P, Sun Y, Wang Y. Org. Lett. 2016; 18: 3154
• 10a Lal GS, Pez GP, Syvret RG. Chem. Rev. 1996; 96: 1737
• 10b Taylor SD, Kotoris CC, Hum G. Tetrahedron 1999; 55: 12431
• 10c Kiselyov AS. Chem. Soc. Rev. 2005; 34: 1031
• 10d Baudoux J, Cahard D. Org. React. 2007; 69: 347
• 10e Liang T, Neumann CN, Ritter T. Angew. Chem. Int. Ed. 2013; 52: 2
• 10f Zhu W, Hu X, Wang F, Yang X, Wu X. Chin. J. Chem. 2015; 33: 220
• 10g Wang W, Chen W, Luo J, Xie P. Chin. J. Org. Chem. 2021; 41: 543
• 11a Trenner J, Depken C, Weber T, Breder A. Angew. Chem. Int. Ed. 2013; 52: 8952
• 11b Deng Z, Wei J, Liao L, Huang H, Zhao X. Org. Lett. 2015; 17: 1834
• 11c Liao L, Guo R, Zhao X. Angew. Chem. Int. Ed. 2017; 56: 3201
• 11d Mei H, Aradi K, Kiss L, Han J. Chin. Chem. Lett. 2023; 34: 108657
• 11e Sun Y.-N, Wang C.-L, Zhang N, Wang Z, Liu Z.-L, Liu J.-L. Chin. Chem. Lett. 2014; 25: 1503
• 12a Zhang X, Guo R, Zhao X. Org. Chem. Front. 2015; 2: 1334
• 12b Cresswell AJ, Eey ST.-C, Denmark SE. Nat. Chem. 2015; 7: 146
• 12c Kratzschmar F, Kaßel M, Delony D, Breder A. Chem. Eur. J. 2015; 21: 7030
• 12d Guo R, Huang J. Huang H., Zhao X. 2016; 18: 504
• 12e Kawamata Y, Hashimoto T, Maruoka K. J. Am. Chem. Soc. 2016; 138: 5206
• 13a Pellegrini C, Strässler C, Weber M, Borschberg HJ. Tetrahedron: Asymmetry 1994; 5: 1979
• 13b White JD, Li Y, Ihle DC. J. Org. Chem. 2010; 75: 3569