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Updated: Apr 18, 2026
A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position
Kohei Moriya1, Dorian Didier, Meike Simon
1Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München (Germany).
Abstract:
Secondary alkyllithium reagents bearing an OTBS group (TBS=tert-butyldimethylsilyl) at the 3-position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3-difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3-siloxy group strongly accelerates the epimerization at the lithium-substituted carbon atom. This method offers a new way to construct chiral open-chain molecules with excellent stereoselectivity.
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