title: Uncovering the mechanistic role of HMPA in the samarium Barbier reaction.
abstract: The presence of HMPA is critical for the selective coupling of alkyl halides and ketones by SmI2. Although previous rate studies have shown that HMPA dramatically accelerates the reduction of alkyl halides over ketones, the basis of this rate acceleration is unknown. In this communication, we report experimental and computational evidence that demonstrate that the selectivity observed in the samarium Barbier reaction is in part a result of activation of the alkyl halide bond by HMPA.
authors.affiliation: Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015, USA.
authors.forename: Kimberly A
authors.initials: KA
authors.lastname: Choquette
authors.forename: Dhandapani V
authors.initials: DV
authors.lastname: Sadasivam
authors.forename: Robert A
authors.initials: RA
authors.lastname: Flowers