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Noble metal-free upgrading of multi-unsaturated biomass derivatives at room temperature: silyl species enable reactivity

Author:
Li, Hu, Zhao, Wenfeng, Dai, Wenshuai, Long, Jingxuan, Watanabe, Masaru, Meier, Sebastian, Saravanamurugan, Shunmugavel, Yang, Song, Riisager, Anders
Source:
Green chemistry 2018 v.20 no.23 pp. 5327-5335
ISSN:
1463-9270
Subject:
ambient temperature, amides, biomass, catalysts, esters, glycols, green chemistry, hydrides, hydrogenation, spectroscopy, value added
Abstract:
Biomass derivatives are a class of oxygen-rich organic compounds, which can be selectively upgraded to various value-added molecules by partial or complete hydrogenation over metal catalysts. Here, we show that Cs₂CO₃, a low-cost commercial chemical, enables the selective reduction of dicarbonyl compounds including bio-derived carboxides to monohydric esters/amides, hydroxylamines or diols with high yields (82–99%) at room temperature using eco-friendly and equivalent hydrosilane as a hydride donor. The in situ formation of silyl ether enables the developed catalytic system to tolerate other unsaturated groups and permits a wide substrate scope with high selectivities. Spectroscopic and computational studies elucidate reaction pathways with an emphasis on the role of endogenous siloxane.
Agid:
6231032