Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation

A new strategy for the functionalization of sterically hindered terminal olefins is reported. Alkenes bearing quaternary carbons at the allylic or homoallylic position are readily oxidized to the corresponding aldehydes by palladium/copper/nitrite catalysis. A broad range of functional groups includ...

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Published inJournal of the American Chemical Society Vol. 138; no. 40; pp. 13179 - 13182
Main Authors Kim, Kelly E, Li, Jiaming, Grubbs, Robert H, Stoltz, Brian M
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 12.10.2016
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Summary:A new strategy for the functionalization of sterically hindered terminal olefins is reported. Alkenes bearing quaternary carbons at the allylic or homoallylic position are readily oxidized to the corresponding aldehydes by palladium/copper/nitrite catalysis. A broad range of functional groups including esters, nitriles, silyl ethers, vinylogous esters, ketones, lactones, and β-ketoesters are tolerated under the reaction conditions. The crude aldehyde products can be transformed further, enabling direct conversion of hindered terminal alkenes to various other synthetically useful functional groups, resulting in formal anti-Markovnikov hydroamination, among other transformations.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b08788