Li+-Controlled Diastereoselectivity of the Addition of Allenyl Cuprate Reagents to Aldehydes

Pierre Mangeney (1) , Hélène Gérard (2) , Emmanuel Vrancken (3)

1 CO - Chimie Organique
2 LCT - Laboratoire de chimie théorique
3 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

This personal account summarizes our recent work regarding the addition of allenyl cuprates to aldehydes. An intertwined experimental and theoretical study enables highlighting of the crucial role of Li+ as a structuring agent in the different intermediates and transition states involved, and thus on the diastereochemical outcome of the reaction.

Mots clés: homopropargylic alcohols - allene - cuprate - lithium - diastereoselectivity - DFT calculations

Domaines: Chimie organique

Pierre Mangeney, Hélène Gérard, Emmanuel Vrancken. Li+-Controlled Diastereoselectivity of the Addition of Allenyl Cuprate Reagents to Aldehydes. Synthesis: Journal of Synthetic Organic Chemistry, 2016, 49 (3), pp.526-531. ⟨10.1055/s-0036-1588613⟩. ⟨hal-01468753⟩