Hydroamination of Unactivated Alkenes with Aliphatic Azides

Autor:	Si-Ming Jia, Yi-Hang Huang, Zhan-Lin Wang, Fang-Xu Fan, Bo-Han Fan, Hao-Xiang Sun, Hao Wang, Fei Wang
Rok vydání:	2022
Předmět:	Azides Colloid and Surface Chemistry Indicators and Reagents General Chemistry Alkenes Silanes Biochemistry Catalysis
Zdroj:	Journal of the American Chemical Society. 144:16316-16324
ISSN:	1520-5126 0002-7863
DOI:	10.1021/jacs.2c07643
Popis:	We report here an efficient and highly diastereoselective intermolecular anti-Markovnikov hydroamination of unactivated alkenes with aliphatic azides in the presence of silane. The system tolerates a wide range of azides and alkenes and operates with alkene as limiting reagent. Mechanistic studies suggest a radical chain pathway that involves aminium radical formation, radical addition to alkenes and HAT from silane to β-aminium alkyl radical. The use of sterically bulky silane is proposed to contribute to the excellent diastereoselectivity for HAT. Computational analysis uncovers the reaction pathway of aliphatic azide activation with silyl radical for aminyl radical formation.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::6d7c0b51f73ab04b2a12c2519925e1f3 https://doi.org/10.1021/jacs.2c07643 Zobrazit plný text záznamu