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Updated: Jul 2, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Selective generation of lithiated benzonitriles: the importance of reaction conditions
Sergiusz Luliński1, Katarzyna Zajac
1Warsaw University of Technology, Faculty of Chemistry, Noakowskiego 3, 00-664 Warsaw, Poland. serek@ch.pw.edu.pl
Abstract:
Lithiated benzonitriles can be generated in high yields from reactions of bromobenzonitriles with n-BuLi in THF under standard cryogenic conditions (ca. -70 degrees C) provided the reverse addition mode is employed. The resultant aryllithiums are fairly stable at temperatures up to -60 degrees C. The formation of lithiated benzonitriles via Br/Li exchange under normal addition mode conditions is plagued by deprotonation and extensive CN-addition reactions. The generation of related aryllithiums from disilylated bromobenzonitriles is comparatively less sensitive to reaction conditions.
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