title: Stereospecific decarboxylative allylation of sulfones.
abstract: Allyl sulfonylacetic esters undergo highly stereospecific, palladium-catalyzed decarboxylative allylation. The reaction allows the stereospecific formation of tertiary homoallylic sulfones in high yield. In contrast to related reactions that proceed at -100 degrees C and require highly basic preformed organometallics, the decarboxylative coupling described herein occurs under mild nonbasic conditions and requires no stoichiometric additives. Allylation of the intermediate alpha-sulfonyl anion is more rapid than racemization, leading to a highly enantiospecific process. Density functional theory calculations indicate that the barrier for racemization is 9.9 kcal/mol, so the barrier for allylation must be <9.9 kcal/mol.
authors: Department of Chemistry, The University of Kansas, 2010 Malott Hall, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, USA.
authors: Jimmie D
authors: JD
authors: Weaver
authors: Being J
authors: BJ
authors: Ka
authors: David K
authors: DK
authors: Morris
authors: Ward
authors: W
authors: Thompson
authors: Jon A
authors: JA
authors: Tunge
mesh_terms: D000478:Alkylation; D003198:Computer Simulation; D003653:Decarboxylation; D015394:Molecular Structure; D013237:Stereoisomerism; D013450:Sulfones / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D013450:Sulfones