title: Direct transacylation of 2,2,2-trihaloethyl esters with amines and alcohols using phosphorus (III) reagents for reductive fragmentation and in situ activation.
abstract: Amides and esters have been synthesized from 2,2,2-trihaloethyl esters in one pot using phosphorus-(III) reagents as reductants, with resultant carboxylate activation as an acyloxyphosphonium intermediate, and in situ trapping by amine or alcohol nucleophiles. Secondary and tertiary amides were synthesized, including a dipeptide, in good yields using hexamethylphosphorous triamide (Me2N)3P, as reducing agent. Optimal yields of esters derived from primary and secondary alcohols were obtained using tributylphosphine and DMAP. Tribromoethyl esters provided yields superior to those obtained with trichloroethyl esters.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison 53706-1369, USA.
authors.forename: J J
authors.initials: JJ
authors.lastname: Hans
authors.forename: R W
authors.initials: RW
authors.lastname: Driver
authors.forename: S D
authors.initials: SD
authors.lastname: Burke
mesh_terms: D000215:Acylation; D000438:Alcohols / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D007202:Indicators and Reagents; D009943:Organophosphorus Compounds; D010084:Oxidation-Reduction
chemical_list: D000438:Alcohols; D000588:Amines; D006846:Hydrocarbons, Halogenated; D007202:Indicators and Reagents; D009943:Organophosphorus Compounds