Figure 1.

Substrate scope of the coupling of S‐(alkynyl) sulfonium salts with lithiated alkynes. All reagents were used in stoichiometric amounts and all reactions were quenched after 15 min. Yields are of the isolated asymmetric di‐ and triynes, in parenthesis the yields of the isolated homocoupling products.^[a] The yield of 2 b was improved to 52 % when 1.0 equiv. of CuCN was added to the reaction mixture under otherwise identical conditions. X‐ray structure of 2 j, ellipsoids shown at 50 % probability and hydrogen atoms omitted for clarity.^[15]