Carbon–Carbon Triple Bond Cleavage to Access Di‐ and Tri‐substituted Alkenes

Utilizing alkynes as feedstocks represents one of the most economical and straightforward strategies for the preparation of alkenes. While conventional strategies typically rely on alkyne addition, the cleavage and reconstruction of the C≡C triple bond to assemble acyclic alkenes remains virtually unexplored. Herein, we report an unprecedented, metal‐free protocol for the skeletal cleavage of alkynes to construct di‐ and trisubstituted alkenes via a tandem Michael addition/Grob fragmentation cascade. Furthermore, terminal alkynes successfully undergo a divergent cleavage cascade, seamlessly furnishing high‐value triarylmethanols.