Conformational study of the intramolecular diels-alder reaction of a pentadienyl acrylate. Theoretical evaluation of kinetic and thermodynamic control
Acrylate 4, prepared from diacetylrhamnal, underwent intramolecular Diels-Alder cycloaddition to give the thermodynamically disfavored trans-fused gamma-lactone 15 as the major product, along with two stereoisomeric cycloadducts. A computational analysis of each of the four transition states arising from 4 and the corresponding cycloadducts permits an understanding of the contrasting requirements for kinetic versus thermodynamic control of the reaction.
White
JD
Departments of Chemistry, Oregon State University, Corvallis, Oregon 97331-4003, and Emory University, Atlanta, Georgia 30322, USA.
Demnitz
FW
Oda
H
Hassler
C
Snyder
JP