Olefin metathesis, one of the most powerful methods used to form C-C bonds, has been applied in the industry to produce valuable olefins, such as propylene and alpha-olefins, involved in the synthesis of polypropylene and detergents, respectively. Another critical application of olefin metathesis, ring-closing metathesis (RCM), is employed to synthesize pharmaceuticals and natural products. Currently used olefin metathesis catalysts are based on second- and third-row metals, including Ru, Mo, W, and Re. A shift to a more abundant metal, vanadium, is desirable for economic and environmental reasons. Recently, we reported the first example of RCM catalyzed by V alkylidene phosphine catalysts. However, the catalyst’s instability towards ethylene prevented their high activity in reactions with terminal olefins. Computational studies showed that the main decomposition pathway is beta-hydride elimination at unsubstituted metallacyclobutane. More recently, we found that the phosphine exchange to N-heterocyclic carbene (NHC) in V alkylidenes significantly disfavors beta-hydride elimination preventing catalyst degradation, and reported the highest productivity in V-based RCM to date. In addition, V alkylidene NHC catalysts can tolerate multiple organic functional groups, which is crucial for introducing V-based olefin metathesis for routine organic synthesis

Vanadium alkylidenes for olefin metathesis

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.