Intramolecular vinylation of secondary and tertiary organolithiums

Julien Lefranc, Anne M. Fournier, Gaëlle Mingat, Simon Herbert, Tommaso Marcelli, Jonathan Clayden*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

36 Citations (Scopus)

Abstract

Deprotonation of benzylic ureas, carbamates, and thiocarbamates bearing N′-alkenyl substituents generates carbanions which undergo intramolecular migration of the alkenyl group to the carbanionic center. Solvolysis of the urea products generates α-alkenylated amines. With an enantiomerically pure starting urea, migration proceeds stereospecifically, generating in enantiomerically enriched form products containing allylic quaternary stereogenic centers bearing N. Computational and in situ IR studies suggest that the reaction, formally a nucleophilic substitution at an sp 2 carbon atom, proceeds by a concerted addition-elimination pathway.

Original languageEnglish
Pages (from-to)7286-7289
Number of pages4
JournalJournal of the American Chemical Society
Volume134
Issue number17
Early online date15 Apr 2012
DOIs
Publication statusPublished - 2 May 2012

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