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Updated: May 14, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Preparation of stereodefined secondary alkyllithium compounds
Stephanie Seel1, Guillaume Dagousset, Tobias Thaler
1Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5-13, Haus F, 81377 München, Germany.
Abstract:
We have developed a practical stereoretentive iodine/lithium-exchange process that allows the stereodefined preparation of cis- and trans-cycloalkyllithium compounds from their corresponding stereodefined iodides. Quenching with electrophiles offers stereospecific access to both cis- (up to 96% cis) and trans-cycloalkyl derivatives (up to 99% trans). A detailed study of the thermodynamic stabilities, stereochemical behavior, and reactivities of axially and equatorially substituted cyclohexyllithium reagents is reported. Ab initio calculations demonstrate that the formation of oligomeric cyclohexyllithium structures is pivotal for explaining the observed stereochemical preference.
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