ChemInform Abstract: S_N2′ versus S_N2 Reactivity: Control of Regioselectivity in Conversions of Baylis—Hillman Adducts.

Abstract

Baylis--Hillman Adducts. -The reaction of allylammonium ions with less than 1 equiv. of the potassium salts of stabilized carbanions affords methylene derivatives under kinetially controlled conditions (SN2' reactions). When more than 1 equiv. of the carbanions is used, a second SN2' reaction converts the methylene compounds into their thermodynamically more stable allyl isomers. The electrophilicity parameters are calculated for the allylammonium ions. The kinetic data indicate the SN2' reactions to proceed via an addition-elimination mechanism with the rate determining addition step. -(BAIDYA, M.; REMENNIKOV, G. Y.; MAYER, P.; MAYR*, H.; Chem. Eur. J. 16 (2010) 4, 1365-1371; Fachbereich Chem. Biochem.,