Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate

Chemistry. 2021 Jul 7;27(38):9919-9924. doi: 10.1002/chem.202100849. Epub 2021 May 27.

Abstract

Performing carbonylation without the use of carbon monoxide for high-value-added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO2 hydrogenation, the protocols represent indirect approaches for chemical valorization of CO2 .

Keywords: formic acid; hydroformylation; hydroxymethylation; linear alcohol; tandem reaction.