First DMAP-mediated direct conversion of Morita-Baylis-Hillman alcohols into γ-ketoallylphosphonates: Synthesis of
Marwa Ayadi1, Haitham Elleuch2, Emmanuel Vrancken3
1Université 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.
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 phosphonate 2a (R = H) gave the corresponding γ-hydroxyallylphosphonate 5 that further reacted with tosylamines in the presence of diiodine (15 mol %) as a catalyst, affording the corresponding SN2-type products 6a-d in 63 to 70% isolated yields. Alternatively, the alcohol 5 produced the corresponding acetate 7 which, mediated by Ce(III), was successfully converted into the corresponding γ-aminoallylphosphonates 8a-d.
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