Mechanistic origin of the stereodivergence in decarboxylative allylation.
A stereochemical test has been used to probe the mechanism of decarboxylative allylation. This probe suggests that the mechanism of DcA reactions can change based on the substitution pattern at the alpha-carbon of the nucleophile; however, reaction via stabilized malonate nucleophiles is the lower energy pathway. Lastly, this mechanistic proposal has predictive power and can be used to explain chemoselectivities in decarboxylative reactions that were previously confounding.
Department of Chemistry, The University of Kansas, Lawrence, Kansas 66045, USA.
Kalicharan
K
Chattopadhyay
Ranjan
R
Jana
Victor W
VW
Day
Justin T
JT
Douglas
Jon A
JA
Tunge
D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D003653:Decarboxylation; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
D000498:Allyl Compounds; D004952:Esters