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RESEARCH ARTICLE
Contents Vol 74(9)

Tandem Oxidation-Dehydrogenation of (Hetero)Arylated Primary Alcohols via Perruthenate Catalysis

Christian J. Bettencourt https://orcid.org/0000-0001-5855-9198 A , Sharon Chow https://orcid.org/0000-0001-8193-3504 A , Peter W. Moore https://orcid.org/0000-0003-0527-4249 A , Christopher D. G. Read https://orcid.org/0000-0002-1967-7287 A , Yanxiao Jiao https://orcid.org/0000-0003-2678-4723 B , Jan Peter Bakker C , Sheng Zhao A , Paul V. Bernhardt https://orcid.org/0000-0001-6839-1763 A and Craig M. Williams https://orcid.org/0000-0002-3834-7398 A D
+ Author Affiliations
- Author Affiliations

A School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, Qld 4072, Australia.

B College of Chemistry and Chemical Engineering, Jiujiang University, Jiujiang, 332005, China.

C Institute for Life Science & Technology, Hanze University Groningen, NL-9747 AS Groningen, Netherlands.

D Corresponding author. Email: c.williams3@uq.edu.au

Australian Journal of Chemistry 74(9) 652-659 https://doi.org/10.1071/CH21137
Submitted: 8 June 2021  Accepted: 11 August 2021   Published: 30 August 2021

Abstract

Tandem oxidative-dehydrogenation of primary alcohols to give α,β-unsaturated aldehydes in one pot are rare transformations in organic synthesis, with only two methods currently available. Reported herein is a novel method using the bench-stable salt methyltriphenylphosphonium perruthenate (MTP3), and a new co-oxidant NEMO·PF6 (NEMO = N-ethyl-N-hydroxymorpholinium) which provides unsaturated aldehydes in low to moderate yields. The Ley-Griffith oxidation of (hetero)arylated primary alcohols with N-oxide co-oxidants NMO (NMO = N-methylmorpholine N-oxide)/NEMO, is expanded by addition of the N-oxide salt NEMO·PF6 to convert the intermediate saturated aldehyde into its unsaturated counterpart. The discovery, method development, reaction scope, and associated challenges of this method are highlighted. The conceptual value of late-stage dehydrogenation in natural product synthesis is demonstrated via the synthesis of a polyene scaffold related to auxarconjugatin B.

Keywords: dehydrogenation, oxidation, MTP3, TPAP, tandem, catalysis, polyene, N-ethylmorpholine N-oxide.


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