title: Three-carbon homologation of diorganozincs with lithiated acetylenic epoxides.
abstract: Reaction of dialkylzincs with lithiated acetylenic epoxides is described to give zincates that undergo a 1,2-metallate rearrangement by an anti-S(N)2' pathway. This rearrangement occurs with the transfer of an alkyl or a silyl group affording allenylzinc intermediates. Allenic and/or homopropargylic alcohols are obtained upon hydrolysis. Quenching the reaction mixture with aldehydes or ketones is shown to give access to 2-alkynyl-1,3-diols in a stereoselective manner.
authors.affiliation: Institut Parisien de Chimie Moléculaire, Institut de Chimie Moléculaire (FR 2769), UPMC-Univ Paris 6, UMR CNRS 7201, Case 183, 4 place Jussieu, F-75252 Paris Cedex 05, France.
authors.forename: Aurélien
authors.initials: A
authors.lastname: Denichoux
authors.forename: Laurent
authors.initials: L
authors.lastname: Debien
authors.forename: Mathieu
authors.initials: M
authors.lastname: Cyklinsky
authors.forename: Malika
authors.initials: M
authors.lastname: Kaci
authors.forename: Fabrice
authors.initials: F
authors.lastname: Chemla
authors.forename: Franck
authors.initials: F
authors.lastname: Ferreira
authors.forename: Alejandro
authors.initials: A
authors.lastname: Pérez-Luna