Generation of Halomethyl Radicals by Halogen Atom Abstraction and Their Addition Reactions with Alkenes

α-Aminoradicals undergo halogen atom abstraction to form halomethyl radicals in reactions initiated by the combination of tert-butyl hydroperoxide, aliphatic trialkylamine, halocarbon, and copper­(I) iodide. The formation of the α-aminoradical circumvents preferential hydrogen atom transfer in favor...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2019-10, Vol.141 (42), p.16643-16650
Main Authors: Neff, Robynne K, Su, Yong-Liang, Liu, Siqi, Rosado, Melina, Zhang, Xinhao, Doyle, Michael P
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:α-Aminoradicals undergo halogen atom abstraction to form halomethyl radicals in reactions initiated by the combination of tert-butyl hydroperoxide, aliphatic trialkylamine, halocarbon, and copper­(I) iodide. The formation of the α-aminoradical circumvents preferential hydrogen atom transfer in favor of halogen atom transfer, thereby releasing the halomethyl radical for addition to alkenes. The resulting radical addition products add the tert-butylperoxy group to form α-peroxy-β,β-dichloropropylbenzene products that are convertible to their corresponding β,β-dichloro-alcohols and to novel pyridine derivatives. Computational analysis clearly explains the deviation from traditional HAT of chloroform and also establishes formal oxidative addition/reductive elimination as the lowest energy pathway.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b05921