Stability of some aryllithiums in the presence of cyano group: Synthesis of biaromatic cyanoarylboronic acids and silanes

Abstract

Lithium diisopropylamine (LDA)-mediated deprotonation reactions of halogenated cyanobenzyloxy-benzenes and cyanobiphenyls were investigated. The resultant organolithium derivatives were converted into the corresponding arylboronic acids or silanes. It was found that the stability of the obtained aryllithiums towards isomerization to the respective benzyllithiums depends strongly on the number of fluorine atoms in the phenyl ring and on the position of the cyano group. Halogenated cyanobiaryls were selectively deprotonated in the position flanked by two halogen atoms; however, the yield depended strongly on the reaction conditions. Addition of LDA to the cyano group was observed on the lithiation of 4-cyano-3',5'-dichlorobiphenyl rather than deprotonation. Copyright © 2012 John Wiley & Sons, Ltd.