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Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

Authors :
Timothy R. Newhouse
Bo-Ran Wang
Hai-Jun Zhang
Liang Yin
Shi-Tao Pan
Alexander W. Schuppe
Jin-Xiang Chen
Source :
Journal of the American Chemical Society. 140:5300-5310
Publication Year :
2018
Publisher :
American Chemical Society (ACS), 2018.

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.

Details

ISSN :
15205126 and 00027863
Volume :
140
Database :
OpenAIRE
Journal :
Journal of the American Chemical Society
Accession number :
edsair.doi.dedup.....30585fd3d7ef886a3094b2f6f0497cc4
Full Text :
https://doi.org/10.1021/jacs.8b01886