Issue 7, 2022

Ru(dppbsa)-catalyzed hydrodeoxygenation and reductive etherification of ketones and aldehydes

Abstract

Methods for the Ru(dppbsa)-catalyzed hydrodeoxygenation and reductive etherification of ketones and aldehydes were developed. Carbonyl substrates without β-CH functionality follow a hydrogenation–hydrogenolysis path, wherein the hydrogenolysis of the alkanol intermediates is the rate-limiting step. By contrast, a hydrogenation–dehydration–hydrogenation path is followed by carbonyl substrates with β-CH functionality, suffering from rate-limiting sulfonate ligand-assisted reversible H2 cleavage. This hydrodeoxygenation is competitive with reductive etherification when using alkanols as hydrogen surrogates. The chemoselectivity can be adjusted based not only on the bond strengths of O–H and C–H bonds in the alkanols but also on the steric hindrance of the carbonyl substrates. As a result, both hydrodeoxygenation and reductive etherification exhibit excellent aldehyde tolerance, while the reductive etherification of ketones is highly hindered based on this protocol.

Graphical abstract: Ru(dppbsa)-catalyzed hydrodeoxygenation and reductive etherification of ketones and aldehydes

Supplementary files

Article information

Article type
Research Article
Submitted
16 Nov 2021
Accepted
14 Feb 2022
First published
14 Feb 2022

Org. Chem. Front., 2022,9, 1943-1954

Ru(dppbsa)-catalyzed hydrodeoxygenation and reductive etherification of ketones and aldehydes

R. Sun, H. Guo, S. Ma, Y. Wang, Z. Yu and B. Xu, Org. Chem. Front., 2022, 9, 1943 DOI: 10.1039/D1QO01717A

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