Preparation and Study of Reusable Polymerized Catalysts for Ester Hydrogenation.

Abstract

A cross-linked catalyst organic framework was prepared by an alternating ring-opening olefin metathesis polymerization between dichloro{N,N′-bis({(2-diphenylphosphino)phenyl}methylidene)bicyclo[2.2.1]-hept-5-ene-2,3-diamine}ruthenium, 1,2-N-di(cis-5-norbornene-2,3-endo-dicarboximido)-ethane, and cis-cyclooctene catalyzed by RuCl2(=CHPh)(PCy3)2 in the presence of a BaSO4 support. The heterogenized catalyst hydrogenated methyl benzoate at a similar rate to the homogeneous catalyst (0.0025 mol % catalyst, 10 mol % KOtBu, 80 °C, 50 atm, tetrahydrofuran, 21 h, ∼15 000 turnovers during the first 1 h). The catalyst was used five times for a total of 121 680 turnovers. A study on the reusability of this catalyst showed that ester hydrogenations with bifunctional catalysts slow as the reaction proceeds. This inhibition is removed by isolating and reusing the catalyst, suggesting that future catalyst design should emphasize avoiding product inhibition.