Synthesis and Diels-Alder reactions of homochiral 2-sulfinylmaleates with cyclopentadiene

Abstract

Enantiomerically pure 2-p-tolylsulfinylmaleates 1, 2 and 3 have been readily prepared by Knoevenagel reaction between (S)-menthyl p-toluenesulfinate and glyoxylic acid. Their asymmetric Diels-Alder reactions with cyclopentadiene have been studied under a wide range of uncatalyzed and catalyzed conditions and the stereochemical results have been explained by assuming a steric control approach, in term of S- cis or S- trans favoured conformations. Uncatalyzed Diels-Alder reactions of 1 and some Lewis acid catalyzed Diels-Alder reactions of 2 show high facial and endo selectivities. The facial selectivity of dienophile 2 highly depends on the Lewis acid, whereas reactivity of 1 and 3 is very sensitive to the solvent. These sulfinylmaleates 1, 2 and 3 act as synthetic equivalents of chiral acetylenedicarboxylates in Diels-Alder reactions after basic elimination of the sulfinylic moiety in the resulting adducts.