title: Dimethylmalonyltrialkylphosphoranes: new general reagents for esterification reactions allowing controlled inversion or retention of configuration on chiral alcohols.
abstract: A new class of trialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence of triethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, solvent, and tuning the electronic and steric nature of the carboxylic acid and steric nature of the phosphorane employed. A coherent mechanism is postulated to explain these observations involving reaction via an initial acyloxyphosphonium ion.
authors.affiliation: Institute of Molecular Catalysis, Department of Chemistry, Brock University, St. Catharines, Ontario L2S 3A1 Canada. jmcnulty@chemiris.labs.brocku.ca
authors.forename: James
authors.initials: J
authors.lastname: McNulty
authors.forename: Alfredo
authors.initials: A
authors.lastname: Capretta
authors.forename: Vladimir
authors.initials: V
authors.lastname: Laritchev
authors.forename: Jeff
authors.initials: J
authors.lastname: Dyck
authors.forename: Al J
authors.initials: AJ
authors.lastname: Robertson