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Pattillo CC, Strambeanu II, Calleja P, et al. Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition. J Am Chem Soc. 2016;138(4):1265-72doi: 10.1021/jacs.5b11294.
Pattillo, C. C., Strambeanu, I. I., Calleja, P., Vermeulen, N. A., Mizuno, T., & White, M. C. (2016). Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition. Journal of the American Chemical Society, 138(4), 1265-72. https://doi.org/10.1021/jacs.5b11294
Pattillo, Christopher C, et al. "Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition." Journal of the American Chemical Society vol. 138,4 (2016): 1265-72. doi: https://doi.org/10.1021/jacs.5b11294
Pattillo CC, Strambeanu II, Calleja P, Vermeulen NA, Mizuno T, White MC. Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition. J Am Chem Soc. 2016 Feb 03;138(4):1265-72. doi: 10.1021/jacs.5b11294. Epub 2016 Jan 25. PMID: 26730458; PMCID: PMC4831720.
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J Am Chem Soc. 2016 Feb 03;138(4):1265-72. doi: 10.1021/jacs.5b11294. Epub 2016 Jan 25.

Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition.

Journal of the American Chemical Society

Christopher C Pattillo, Iulia I Strambeanu, Pilar Calleja, Nicolaas A Vermeulen, Tomokazu Mizuno, M Christina White

Affiliations

  1. Roger Adams Laboratory, Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.

PMID: 26730458 PMCID: PMC4831720 DOI: 10.1021/jacs.5b11294

Abstract

An efficient aerobic linear allylic C-H amination reaction is reported under palladium(II)/bis-sulfoxide/Brønsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with reduced Pd(II)/bis-sulfoxide catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant. Pd(II)/BQ π-acidic interactions have been invoked in various catalytic processes and are often considered beneficial in promoting reductive functionalizations. When such electrophilic activation for functionalization is not needed, however, BQ at high concentrations may compete with crucial ligand (bis-sulfoxide) binding and inhibit catalysis. Kinetic studies reveal an inverse relationship between the reaction rate and the concentration of BQ, suggesting that BQ is acting as a ligand for Pd(II) which results in an inhibitory effect on catalysis.

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