Iron-Catalyzed Three-Component Asymmetric Carboazidation of Alkenes with Alkanes and Trimethylsilyl Azide

Abstract

The fusion of transition-metal catalysis with radical chemistry provides a versatile platform for the asymmetric radical carboazidation of alkenes to enable the rapid assembly of highly functionalized chiral azide compounds. Here, we present an iron-catalyzed asymmetric three-component radical carboazidation that processes electron-deficient alkenes by direct activation of aliphatic C–H bonds. This strategy provides access to a range of valuable chiral azides from readily available chemical feedstocks bearing a tetrasubstituted carbon stereocenter, and their synthetic potential is further showcased through straightforward transformations to provide other valuable enantioenriched building blocks.

Key words

carboazidation - hydrocarbons - ligands - asymmetric synthesis - radical ligand transfer - trimethylsilyl azide

Publikationsverlauf

Eingereicht: 21. Mai 2024

Angenommen nach Revision: 25. Juni 2024

Accepted Manuscript online:
25. Juni 2024

Artikel online veröffentlicht:
17. Juli 2024

• References

• 1a Yi H, Zhang GT, Wang HM, Huang ZY, Wang J, Singh AK, Lei AW. Chem. Rev. 2017; 117: 9016
• 1b Capaldo L, Ravelli D, Fagnoni M. Chem. Rev. 2022; 122: 1875
• 1c Cao H, Kong DG, Yang L.-C, Chanmungkalakul S, Liu T, Piper JL, Peng ZH, Gao LL, Liu XG, Hong X, Wu J. Nat. Synth. 2022; 1: 794
• 2a Zhang W, Wang F, McCann SD, Wang DH, Chen PH, Stahl SS, Liu GS. Science 2016; 353: 1014
• 2b Murphy JJ, Bastida D, Paria S, Fagnoni M, Melchiorre P. Nature 2016; 532: 218
• 2c Yu H, Zhan T, Zhou Y, Chen L, Liu X, Feng X. ACS Catal. 2022; 12: 5136
• 3a Scriven EF. V, Turnbull K. Chem. Rev. 1988; 88: 297
• 3b Brase S, Gil C, Knepper K, Zimmermann V. Angew. Chem. Int. Ed. 2005; 44: 5188
• 4a Ge L, Chiou M.-F, Li Y, Bao H. Green Synth. Catal. 2020; 1: 86
• 4b Sivaguru P, Ning YQ, Bi X. Chem. Rev. 2021; 121: 4253
• 5a Ma X, Chiou M.-F, Ge L, Li X, Li Y, Wu L, Bao H. Chin. J. Catal. 2021; 42: 1634
• 5b Bian K.-J, Nemoto DJr, Kao S.-C, He Y, Li Y, Wang X.-S, West JG. J. Am. Chem. Soc. 2022; 144: 11810
• 6a Ge L, Zhou H, Chiou M.-F, Jiang H, Jian W, Ye C, Li X, Zhu X, Xiong H, Li Y, Song L, Zhang X, Bao H. Nat. Catal. 2020; 4: 28
• 6b Liu W, Pu M, He J, Zhang TH, Dong S, Liu X, Wu Y, Feng X. J. Am. Chem. Soc. 2021; 143: 11856
• 7a Li Y, Lei M, Gong L. Nat. Catal. 2019; 2: 1016
• 7b Jin Y, Fan L.-F, Ng EW. H, Yu L, Hirao H, Gong L.-Z. J. Am. Chem. Soc. 2023; 145: 22031
• 8a Bunescu A, Ha TM, Wang Q, Zhu J. Angew. Chem. Int. Ed. 2017; 56: 10555
• 8b Li W.-Y, Wu C.-S, Wang Z, Luo Y. Chem. Commun. 2018; 54: 11013
• 8c Xu L, Chen J, Chu L. Org. Chem. Front. 2019; 6: 512
• 9 Ge L, Wang H, Liu Y, Feng X. J. Am. Chem. Soc. 2024; 146: 13347

For reviews on chiral N,N′-dioxides, see:
• 10a Liu X, Lin L, Feng X. Acc. Chem. Res. 2011; 44: 574
• 10b Liu X, Lin L, Feng X. Org. Chem. Front. 2014; 1: 298
• 10c Liu X, Zheng H, Xia Y, Lin L, Feng X. Acc. Chem. Res. 2017; 50: 2621
• 10d Liu X, Dong SX, Lin LL, Feng X. Chin. J. Chem. 2018; 36: 791
• 10e Dong S, Liu X, Feng X. Acc. Chem. Res. 2022; 55: 415
• 10f Chen D.-F, Gong L.-Z. Org. Chem. Front. 2023; 10: 3676
• 10g He Y.-M, Cheng Y.-Z, Duan YD, Zhang Y.-D, Fan Q.-H, You S.-L, Luo SZ, Zhu S.-F, Fu X.-F, Zhou Q.-L. CCS Chem. 2023; 5: 2685
• 11a Bian K.-J, Kao S.-C, Nemoto DJr, Chen X.-W, West JG. Nat. Commun. 2022; 13: 7881
• 11b Hooson JF, Tran HN, Bian K.-J, West JG. Chem. Commun. 2024; 60: 3705
• 12a Lee W.-CC, Zhang XP. Trends Chem. 2022; 4: 850
• 12b Lee W.-CC, Wang D.-S, Zhu YL, Zhang XP. Nat. Chem. 2023; 15: 1569
• 12c Lee W.-CC, Zhang XP. Angew. Chem. Int. Ed. 2024; 63: e202320243