Ruthenium triphos complexes [Ru(X(CH2PPh2)3-κ3-P)(NCCH3)3](OTf)2; X = H3C-C, N) as catalysts for the conversion of furfuryl acetate to 1,4-pentanediol and cyclopentanol in aqueous medium

Abstract

The ruthenium complexes [Ru(H3CC(CH2PPh2)3-κ3-P)(NCCH3)3](OTf)2 (1, (H3CC(CH2PPh2)3 = triphos) and [Ru(N(CH2PPh2)3-κ3-P)(NCCH3)3](OTf)2 (2, N(CH2PPh2)3 = N-triphos) have been evaluated as homogeneous ionic hydrogenation catalysts for the catalytic hydrodeoxygenation of furfuryl alcohol and furfuryl acetate to 1,4-pentanediol and cyclopentanol in aqueous media reaction mixtures. For furfuryl alcohol, only marginal yields of 1,4-pentanediol could be achieved with mass balance deficiencies due to humin formation ranging from 67% to 90%. Attempts to improve the catalytic activity of 2 by enhancing its water solubility by nitrogen protonation and (or) methylation failed. Employing the less self-reactive furfuryl acetate as the substrate substantially diminishes humin formation, yielding up to 43% of 1,4-pentanediol and 19% of cyclopentanol (via Piancatelli rearrangement) with 1 and up to 33% of 1,4-pentanediol and 5% of cyclopentanol with 2. A design of experiments study was used to determine and compare the yield responses of the multiple parallel reaction channels with 1,4-pentanediol, cyclopentanol, and humins as a function of reaction temperature, time, catalyst load, and substrate concentration. This explores the correlations between these parameters and their impact on the reaction outcome and suggests an extremely complex overall reaction cascade of interdependent pathways of both acid- and metal-catalyzed steps with some significant differences emerging between the two catalysts.