title: Theoretical study of intramolecular aldol condensation of 1, 6-diketones: trimethylsilyl substituent effect
abstract: Diastereoselective intramolecular aldol condensations are investigated in an experimental and computational study of 1, 6-diketones. Ab initio results show the importance of the acid medium and disapprove the possibility of a spontaneous cyclization, even for silylated compounds. The combination of both experimental and computational approaches brings valuable information on the mechanism and on the selectivity of the aldol reaction. It is found that the enolization of the diketone is a key step in acid-catalyzed mechanism. The cyclization step bears a very small activation energy. The dehydration of the aldols are discussed.
authors.affiliation: UMR 6519, Universite de Reims Champagne-Ardenne/CNRS, UFR Sciences BP 1039, F-51687 REIMS Cedex 2, France.
authors.initials: JP
authors.lastname: Bouillon
authors.initials: C
authors.lastname: Portella
authors.initials: J
authors.lastname: Bouquant
authors.initials: S
authors.lastname: Humbel