Sulfinyl-mediated stereoselective Overman rearrangements and Diels-Alder cycloadditions.

The Overman rearrangement of allylic sulfinyl trichloroacetimidates affords sulfinyl trichloroacetamides with high stereoselectivity and excellent yields. Bis-allylic substrates lead to amido 2-sulfinyl butadiene derivatives in excellent yields, with total chemo- and diastereoselectivity. The Diels-Alder cycloaddition of related dienes is controlled by the sulfoxide moiety.