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. 2013 Jun 21;15(12):3034-7.
doi: 10.1021/ol401220b. Epub 2013 Jun 4.

Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes

Timothy W Liwosz  1 , Sherry R Chemler
Affiliations

Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes

Timothy W Liwosz et al. Org Lett. .

Abstract

We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

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Figures

Scheme 1
Scheme 1
Stoichiometric and Catalytic TEMPO-Capture Reactions Fensterbank’s conditions: Cu(eh)2 (1.2 equiv), TEMPO, DMSO, 120 °C, 20 h (73% yield). Our conditions: Cu(eh)2 (20 mol %), TEMPO, O2 (1 atm), DCE, 105 °C, 24 h (77% yield).
Scheme 2
Scheme 2
Proposed Mechanism
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