title: Convergent diastereoselective preparation of adjacent quaternary stereocenters in an acyclic system.
abstract: The combined carbometalation-zinc homologation-allylation reaction of the resulting stereodefined 3,3-disubstituted allylmetal species with ketones allow the preparation of allylic vicinal diol derivatives in good yields with excellent diastereomeric ratios from commercially available alkynes. Two adjacent quaternary centers are formed with the concomitant formation of three new carbon-carbon bonds in a single-pot operation in an acyclic system. The bulky substituent of the ketone occupies a pseudo-axial position in the Zimmerman-Traxler transition state.
authors.affiliation: The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
authors.forename: Tom
authors.initials: T
authors.lastname: Mejuch
authors.forename: Bishnu
authors.initials: B
authors.lastname: Dutta
authors.forename: Mark
authors.initials: M
authors.lastname: Botoshansky
authors.forename: Ilan
authors.initials: I
authors.lastname: Marek