Premium
Thorpe–Ingold Effect in Branch‐Selective Alkylation of Unactivated Aryl Fluorides
Author(s) -
O'Neill Matthew J.,
Riesebeck Tim,
Cornella Josep
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201804479
Subject(s) - aryl , electrophile , alkylation , chemistry , combinatorial chemistry , reagent , catalysis , selectivity , organic chemistry , alkyl
Presented herein is a general protocol for the alkylation of simple aryl fluorides with unbiased secondary Grignard reagents by means of nickel catalysis. This study revealed a general Thorpe–Ingold effect in the ligand backbone which confers a high degree of selectivity for the secondary carbon center in the C−C coupling event. This protocol is characterized by mild reaction conditions, robustness, and simplicity. Both electron‐rich and electron‐deficient aryl fluorides are suitable candidates in this transformation. Equally amenable are a variety of heterocycles, permitting the coupling without over alkylation at the electrophilic sites.