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Pure Appl. Chem., 2000, Vol. 72, No. 9, pp. 1671-1683

Stereoselective and enantioselective synthesis of five-membered rings via conjugate additions of allylsulfone carbanions

Alfred Hassner, Eugene Ghera, Tamar Yechezkel, Victoria Kleiman, Thiagarajan Balasubramanian and Daryl Ostercamp

Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel

Abstract: This lecture describes some of our studies of lithio derivatives of allyl sulfone carbanions which add α-regioselectively as well as anti diastereoselectively to Michael acceptor olefins. This can be ascribed to chelation in the Michael addition step. When the reaction leads to subsequent ring closure by using a bromoallyl sulfone, the latter acts as a methylenemethane synthon in a (3+2) Michael-initiated ring closure, affording highly functionalized cyclopentane derivatives. Such additions proceed with high stereoselectivity and with asymmetric induction leading to nonracemic substituted cyclopentanones. Additions of allyl sulfone carbanions also proceed stereoselectively to C=N systems containing a chiral auxiliary on N. These can be used in the synthesis of optically active five- and six-membered ring N-heterocycles. Furthermore, chiral groups on the allyl sulfone moiety can induce significant remote asymmetric induction, made possible by the presence of an aromatic π-system which promotes intramolecular chelation to the Li cation.