Cross and Ring-Closing Metathesis of 1,3-Diynes: Metallotropic [1,3]-Shift of Ruthenium Carbenes

摘要

We have demonstrated that the CM of 1,3-diynes provides excellent regioselectivity, which does not depend on the substituents on the alkynes, whereas the E/Z-selectivity showed strong dependency on the substituent. The RCM of substrates possessing a 1,3-diyne moiety undergoes smooth ring closure followed by facile metallotropic [1,3]-shift to give products that contain fully conjugated 1,5-diene-3-ynes. Further exploration of mechanistic and synthetic aspects of this bond reorganization process is in progress.