Pd nanoparticles on green support as dip-catalyst: a facile transfer hydrogenation of olefins and N-heteroarenes in water

Abstract

Chemo- and regioselective hydrogenation methods using highly green sources, particularly from metal nanoparticles on plant stem as support and water, is an intensive research area, which is highly relevant to the development of green chemistry and technology in the 21^st century. Here, the synthesis and activity of a heterogeneous catalytic system (called “dip-catalyst”) for the transfer hydrogenation of a series of styrenyl, unfunctionalized olefins, quinoline and other N-heteroarenes, are presented. It consists of Pd nanoparticles (15–20 nm) anchored on bio-processed jute plant (Corchorus genus) stem as the support. Pd nanoparticles were decorated on the green support (GS) jute stem by the in situ reduction of K₂PdCl₄ in aqueous medium at 70 °C, using formic acid as the reductant. The Pd@GS was characterized using SEM, EDS, XRD, FTIR, XPS and TEM. Elemental mapping revealed uniform distribution of Pd on the cellulose matrix of the jute stem. The catalyst was successfully applied to the chemoselective transfer hydrogenation of numerous styrenyl, unfunctionalized olefins. Its high functional group tolerance was investigated during the olefins hydrogenation in water. Furthermore, Pd@GS was capable of quantitative hydrogenation to selectively produce 1,2,3,4-tetrahydroquinoline (THQ) in water using stoichiometric amounts of tetrahydroxydiboron (THDB) at 60 °C with turn over frequency (TOF) 4938 h⁻¹. This system is stable in water and displays excellent recyclability; it could be used for 32 consecutive cycles, without losing its original crystallinity or requiring replenishment.