Synthesis of Unprotectedα-Tertiary Amines and 1,2-Amino Alcohols from Vinyl Azides by Light Induced Denitrogenative Alkylarylation/Dialkylation  

作　　者：Sifan Li Hai-Wu Du Paul W.Davies Wei Shu 

机构地区：[1]Department of Chemistry,Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen 518055,Guangdong [2]School of Chemistry,University of Birmingham,Edgbaston,Birmingham B152TT

出　　处：《CCS Chemistry》2024年第4期1060-1070,共11页中国化学会会刊（英文）

基　　金：This research was made possible as a result of a generous grant from NSFC(grant nos.21971101 and 22171127);Guangdong Basic and Applied Basic Research Foundation(grant no.2022A1515011806);Department of Education of Guangdong Province(grant nos.2022JGXM054 and 2021KTSCX106);Shenzhen Science and Technology Innovation Committee(grant no.JCYJ20220519201425001);Thousand Talents Program for Young Scholars,The Pearl River Talent Recruitment Program(grant no.2019QN01Y261);Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002).

摘　　要：Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.

关 键 词：PHOTOCATALYSIS α-tertiary primary amines 1 2-amino alcohols vinyl azide electron donor-acceptor complex 

分 类 号：O62[理学—有机化学]