Stereospecific decarboxylative allylation of sulfones.
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.
Weaver
Jimmie D
JD
Department of Chemistry, The University of Kansas, 2010 Malott Hall, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, USA.
Ka
Being J
BJ
Morris
David K
DK
Thompson
Ward
W
Tunge
Jon A
JA
D000478:Alkylation; D003198:Computer Simulation; D003653:Decarboxylation; D015394:Molecular Structure; D013237:Stereoisomerism; D013450:Sulfones / Q000138:chemical synthesis* / Q000737:chemistry
D013450:Sulfones