4.6 Article

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

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 38, Pages 9919-9924

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202100849

Keywords

formic acid; hydroformylation; hydroxymethylation; linear alcohol; tandem reaction

Funding

  1. National Natural Science Foundation of China [21776296, 21905291]
  2. National Key Research and Development Program of China [2017YFB0602203]
  3. Strategic Priority Research Program of the Chinese Academy of Sciences [XDA21090201]
  4. Shanghai Sailing Program [19YF1453000]

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The study presents a method for producing linear aldehydes or alcohols using formic acid as both carbon monoxide and hydrogen source. Under single Rh catalyst, the linear-selective hydroformylation of alkenes proceeds smoothly with up to 88% yield and >30 regioselectivity. Introducing Ru into the system enables efficient hydroxymethylation with dual Rh/Ru catalysts.
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.

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