First DMAP-mediated direct conversion of Morita-Baylis-Hillman alcohols into ?-ketoallylphosphonates: Synthesis of ?-aminoallylphosphonates.

ABSTRACT: An efficient synthesis of a series of ?-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 ?-hydroxyallylphosphonate 5 that further reacted with tosylamines in the presence of diiodine (15 mol %) as a catalyst, affording the corresponding S_N2-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 ?-aminoallylphosphonates 8a-d.

SUBMITTER: Ayadi M 

PROVIDER: S-EPMC5238584 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature