Mechanistic and synthetic aspects of the reaction of gamma-halogeno-alpha,beta-unsaturated ketones and esters with simple trialkyl phosphites.

Abstract

Phosphorylation of different gamma-halogeno-alpha,beta-unsaturated ketones, ketoesters and diesters 11a-h with simple trialkyl phosphites gives 1,3-dienylphosphates 14, cyclopropylphosphonates 15, ketovinylphosphonates 17 and other products depending on the nature and number of activating groups and halogen atoms in the substrate. Most likely the reaction proceeds via oxaphospholene 23 which is in equilibrium with pseudorotamer 24 and an open, dipolar form 22. Dipolar form 33 is a likely intermediate when two activating groups are present.