title: Stereodivergent Aminocatalytic Synthesis of Z- and E-Trisubstituted Double Bonds from Alkynals.
abstract: A highly diastereoselective synthesis of trisubstituted Z- or E-enals, which are important intermediates in organic synthesis, as well as being present in natural products, is described using different alkynals and nucleophiles as starting materials. Diastereocontrol is mainly governed by the appropriate catalyst. Therefore, those reactions controlled by steric effects, such as the Jørgensen-Hayashi's catalyst, give access to E isomers, and those catalysts that facilitate hydrogen bonding, such as tetrazol-pyrrolidine Ley's catalyst, allow the synthesis of Z isomers. A stereochemical model based on DFT calculations is proposed.
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.
authors.forename: Leyre
authors.initials: L
authors.lastname: Marzo
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.
authors.forename: Javier
authors.initials: J
authors.lastname: Luis-Barrera
authors.affiliation: Departamento de Química Inorgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.
authors.forename: Rubén
authors.initials: R
authors.lastname: Mas-Ballesté
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain.
authors.forename: José Luis García
authors.initials: JL
authors.lastname: Ruano
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain. jose.aleman@uam.es.
authors.forename: José
authors.initials: J
authors.lastname: Alemán
keywords: alkynals; aminocatalysis; double bonds; enals; protonation