Open Accessδ-C–H Mono- and Dihalogenation of Alcohols
Author(s) -
Alastair N. Herron,
Dongxin Liu,
Guoqin Xia,
JinQuan Yu
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.9b13171
Subject(s) - chemistry , oxidizing agent , radical , alkoxy group , hydrogen peroxide , hydrogen atom abstraction , halogen , photochemistry , peroxide , combinatorial chemistry , surface modification , organic chemistry , alkyl
Alkoxy radicals have long been known to enable remote C-H functionalization via 1,5-hydrogen atom abstraction. However, methods for their generation traditionally have relied upon highly oxidizing metals, ultraviolet radiation, or preformed peroxide intermediates, which has prevented the development of many desirable transformations. Herein we report a new bench-stable precursor that decomposes to free alkoxy radicals via a previously unreported single-electron oxidation pathway. This new precursor enables the fluorination and chlorination of remote C-H bonds under exceptionally mild conditions with exceedingly high monoselectivity. Iterative use of this precursor enables the introduction of a second halogen atom, granting access to remote dihalide motifs, including CF 2 and CFCl.