α-Tertiary Dialkyl Ether Synthesis via Reductive Photocatalytic α-Functionalization of Alkyl Enol Ethers

被引：29

作者：

Leitch, Jamie A. ^{[1
]}

Rossolini, Thomas ^{[1
]}

Rogova, Tatiana ^{[1
]}

Dixon, Darren J. ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Oxford OX1 3TA, England

来源：

ACS CATALYSIS | 2020年 / 10卷 / 19期

基金：

加拿大自然科学与工程研究理事会; 英国工程与自然科学研究理事会;

关键词：

ether; photoredox catalysis; reductive; radicals; quaternary center; C-H FUNCTIONALIZATION; CARBOXYLIC-ACID; RADICALS; CATALYSIS; DERIVATIVES; ACTIVATION; REACTIVITY; ESTERS; FE;

D O I：

10.1021/acscatal.0c02584

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The photocatalytic construction of C(sp(3))-rich alpha-tertiary dialkyl ethers through the reductive alpha-functionalization of alkyl enol ether substrates with conjugated alkenes in the presence of a Hantzsch ester terminal reductant under blue LED irradiation is described. Pivoting on oxocarbenium ion generation via an initial TMSCl-facilitated protic activation of the enol ether substrate, subsequent single-electron transfer to this intermediate delivers the putative nucleophilic alpha-oxy tertiary radical capable of productively combining with a variety of alkene substrates. The reductive functionalization strategy was simple to perform, efficient, broad in scope with respect to both alkene acceptor and enol ether donor fragments, and delivered a wide range of complex alpha-tertiary dialkyl ether architectures.

引用

页码：11430 / 11437

页数：8

共 78 条

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