title: Highly efficient transfer of chirality from macrocyclic conformation in the tandem oxy-Cope/Claisen/ene reaction.
abstract: We report three highly stereoselective pericyclic reactions occurring in cascade leading to the synthesis of Decalins skeletons possessing two contiguous quaternary centers. The tandem reaction is triggered by an oxy-Cope rearrangement to create in situ a 10-membered ring enol ether macrocyle 6, which immediately rearranges via a Claisen [3,3] shift to the corresponding E-cyclodec-6-en-1-one 7. The latter spontaneously cyclizes via a transannular ene reaction to produce Decalin 5. Analysis of the mechanism with respect to the origin of the high diastereoselectivity of the tandem oxy-Cope/Claisen/ene reaction is presented.
authors.affiliation: Department of Chemistry, 10 Marie Curie, University of Ottawa, Ottawa, Canada K1N 6N5.
authors.forename: Effiette L O
authors.initials: EL
authors.lastname: Sauer
authors.forename: Louis
authors.initials: L
authors.lastname: Barriault