title: First DMAP-mediated direct conversion of Morita-Baylis-Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates.
abstract: An efficient synthesis of a series of γ-ketoallylphosphonates through a direct conversion of both primary and secondary Morita-Baylis-Hillman (MBH) alcohols by trialkyl phosphites with or without DMAP, used as additive, and under solvent-free conditions, is described herein for the first time. Subsequently, a highly regioselective Luche reduction of the primary phosphonate2a(R = H) gave the corresponding γ-hydroxyallylphosphonate5that further reacted with tosylamines in the presence of diiodine (15 mol %) as a catalyst, affording the corresponding SN2-type products6a-din 63 to 70% isolated yields. Alternatively, the alcohol5produced the corresponding acetate7which, mediated by Ce(III), was successfully converted into the corresponding γ-aminoallylphosphonates8a-d.
authors.affiliation: Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie Organique Structurale LR99ES14, Campus Universitaire, 2092 Tunis, Tunisie; Institut Charles Gerhardt UMR 5253 CNRS-UM-ENSCM, 8 rue de l'Ecole Normale 34296 Montpellier Cedex 5, France.
authors.forename: Marwa
authors.initials: M
authors.lastname: Ayadi
authors.affiliation: Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie Organique Structurale LR99ES14, Campus Universitaire, 2092 Tunis, Tunisie.
authors.forename: Haitham
authors.initials: H
authors.lastname: Elleuch
authors.affiliation: Institut Charles Gerhardt UMR 5253 CNRS-UM-ENSCM, 8 rue de l'Ecole Normale 34296 Montpellier Cedex 5, France.
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Vrancken
authors.affiliation: Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie Organique Structurale LR99ES14, Campus Universitaire, 2092 Tunis, Tunisie.
authors.forename: Farhat
authors.initials: F
authors.lastname: Rezgui
keywords: Arbuzov reaction; allylic substitution; organophosphorus chemistry; γ-aminoallylphosphonate; γ-ketoallylphosphonate