Under solvent-free conditions and at 80 °C, a DMAP- or imidazole-mediated clean and rapid conversion of cyclic Morita-Baylis-Hillman (MBH) acetates into the corresponding γ-keto allyl phosphonates in 70-93% yields is described herein. This allylic nucleophilic substitution works well with primary and secondary acetates bearing, at the β'-position, linear or branched alkyl groups and aryl groups.

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.

Cyclic Morita—Baylis—Hillman acetates are rapidly transformed into the corresponding γ‐keto allyl phosphonates by allylic nucleophilic substitution.

An interesting γ-carbonyl effect permits the dual iron/boron-catalyzed direct nucleophilic substitution of functionalized primary allylic­ alcohols with a large variety of nucleophiles. The resulting substitution products are useful synthetic platforms for heterocycle synthesis, as illustrated in a ready access to tetrahydroisoindol-4-ones.