Successful Cyclopolymerization of 1,6-Heptadiynes Using First-Generation Grubbs Catalyst Twenty Years after Its Invention: Revealing a Comprehensive Picture of Cyclopolymerization Using Grubbs Catalysts

Abstract

Cyclopolymerization (CP) of 1,6-heptadiynes using olefin metathesis catalysts is a useful method for producing various conjugated polyenes. Unfortunately, commercially available user-friendly Grubbs catalysts have long been known to be inactive toward CP. However, recent mechanistic studies revealed that the problem did not lie with the intrinsic activities of Grubbs catalysts but the stability of the propagating carbenes, as decomposed carbene species catalyzed a [2 + 2 + 2] cycloaddition side reaction instead of CP. Fortunately, by adding weakly coordinating ligands such as pyridines as stabilizers, a highly active and fast-initiating third-generation Grubbs catalyst could successfully promote living CP. However, there was no report of CP using the much cheaper but less active first-generation Grubbs catalyst (G1), which has been widely used for more than 20 years. Believing that G1 should also be able to catalyze CP, we came up with three strategies to enhance the activity of G1 toward CP. By categoriz...