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 (CH 3 ) 2 Zn/TiCl 4 or (CH 3 ) 3 Al. 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.