Highly diastereoselective cycloaddition reactions of variously substituted 1-thia- and 1-thia-3-aza-buta-1,3-dienes. Synthesis of enantiomerically pure 5,6-dihydro-4 H-[1,3]thiazines and 3,4-dihydro-2 H-thiopyrans

Abstract

The cycloaddition of 2- or 2,3-substituted 1-thia- and 1-thia-3-aza-4-dimethylamino-buta-1,3-dienes with various dienophiles in the presence of a Lewis acid provides a rapid and diastereoselective access to the 3,4-dihydro-2 H-thiopyran and 5,6-dihydro-4 H-[1,3]thiazine backbones. The generally observed trans relationship between the two newly created strereogenic centres was demonstrated to be the expression of a thermodynamic control of the reaction. The use of chiral dienophile derived from chiral oxazolidin-2-ones allowed us to prepare enantiopure 5,6-dihydro-4 H-[1,3]thiazines and 3,4-dihydro-2 H-thiopyrans. In the asymmetric synthetic process the chiral auxiliary removal step was best accomplished in the presence of samarium triflate in methanol.