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Direct Nucleophilic Substitution Reaction of Cage B−H Bonds by Grignard Reagents: A Route to Regioselective B4‐Alkylation of o ‐Carboranes
Author(s) -
Tang Cen,
Zhang Jiji,
Xie Zuowei
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201702347
Subject(s) - regioselectivity , chemistry , nucleophilic aromatic substitution , steric effects , alkylation , nucleophilic substitution , nucleophile , substitution reaction , alkyl , reagent , aryl , electrophilic aromatic substitution , medicinal chemistry , stereochemistry , organic chemistry , catalysis
Direct nucleophilic substitution reaction of cage B−H bonds of o ‐carboranes by Grignard reagents in the absence of any transition metals has been achieved for the first time, and leads to the regioselective synthesis of a series of 4‐alkyl‐1,2‐diaryl‐ o ‐carboranes in very high yields. The presence of two electron‐withdrawing aryl groups on the cage carbon atoms is crucial to realizing the reaction. The regioselectivity is controlled by both electronic and steric factors. This work represents a new strategy for the development of methods for carborane functionalization.