Ruthenium alkylidene-catalyzed reaction of 1,6-heptadiynes with alkenes

J Org Chem. 2015 Feb 20;80(4):2436-42. doi: 10.1021/jo5028084. Epub 2015 Feb 11.

Abstract

Ruthenium carbene catalysts are able to catalyze cross [2 + 2 + 2] cyclotrimerizations of 1,6-diynes with cyclic and acyclic double bonds. A plausible mechanistic competition is described in which electron-deficient alkenes follow similar pathways as those of other ruthenium catalysts previously utilized and produce mixtures of trienes and cyclohexadienes. On the contrary, allylethers give different isomers of the same final products, suggesting that a metathetic cascade pathway operates in these cases.