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. 2018 Apr 18;140(15):5300-5310.
doi: 10.1021/jacs.8b01886. Epub 2018 Apr 9.

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

Hai-Jun Zhang  1 , Alexander W Schuppe  2 , Shi-Tao Pan  1 , Jin-Xiang Chen  1 , Bo-Ran Wang  1 , Timothy R Newhouse  2 , Liang Yin  1
Affiliations

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

Hai-Jun Zhang et al. J Am Chem Soc. .

Abstract

A mild and operationally simple copper-catalyzed vinylogous aerobic oxidation of β,γ- and α,β-unsaturated esters is described. This method features good yields, broad substrate scope, excellent chemo- and regioselectivity, and good functional group tolerance. This method is additionally capable of oxidizing β,γ- and α,β-unsaturated aldehydes, ketones, amides, nitriles, and sulfones. Furthermore, the present catalytic system is suitable for bisvinylogous and trisvinylogous oxidation. Tetramethylguanidine (TMG) was found to be crucial in its role as a base, but we also speculate that it serves as a ligand to copper(II) triflate to produce the active copper(II) catalyst. Mechanistic experiments conducted suggest a plausible reaction pathway via an allylcopper(II) species. Finally, the breadth of scope and power of this methodology are demonstrated through its application to complex natural product substrates.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1
Copper-Catalyzed Vinylogous Aerobic Oxidation of β,γ-Unsaturated Compounds and Undesired Oxidation Pathways
Scheme 2
Scheme 2
Vinylogous Aerobic Oxidation of 2a under the Reported Reaction Conditions (1H NMR Yields Are Given)
Scheme 3
Scheme 3
Copper-Catalyzed Bisvinylogous and Trisvinylogous Aerobic Oxidation under an Air Atmosphere
Scheme 4
Scheme 4
Catalytic Vinylogous Aerobic Oxidation of (E/Z)-β,γ-Unsaturated Esters and (E/Z)-α,β-Unsaturated Esters (1H NMR Yields Are Given)
Scheme 5
Scheme 5
18O Labeling Experiment
Scheme 6
Scheme 6
Treatment of Product 7a with the Reaction Conditions
Scheme 7
Scheme 7
Efforts to Capture a Peroxide Species through an Intramolecular Oxa-Michael Addition
Scheme 8
Scheme 8
Proposed Mechanism for the Copper-Catalyzed Aerobic Vinylogous Oxidation
Scheme 9
Scheme 9
Copper-Catalyzed 10 g-Scale Vinylogous Aerobic Oxidation
Scheme 10
Scheme 10
Application of the Present Catalytic Vinylogous Aerobic Oxidation to Structure Modification and Total Synthesis of Natural Products
See this image and copyright information in PMC

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