Regio‐ and Stereoselective Carbosulfenylation of Olefins

In a one-pot procedure, cyclic olefins such as 1, n = 1–3, can be transformed stereospecifically into the trans-substituted products 2 by chlorosulfenylation followed by alkylation with Lewis acidic organometallic reagents such as (CH3)2Zn/TiCl4 or (CH3)3Al. This reaction concept can be extended to trisubstituted olefins and α-chiral 1,2-disubstituted olefins, such as 3, high regio- and stereoselectivity being achieved in the latter case (formation of 4). The interplay of 1,2-asymmetric induction and trans stereospecificity leads to defined 1,3-stereorelationships.