Aerobic Palladium-Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite

Abstract

Catalytic nitrite was found to enable carbon–oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. A variety of functional groups were tolerated, and high yields (up to 94 %) were observed with many substrates, also for a multigram-scale reaction. Nitrogen dioxide, which could form from nitrite under the reaction conditions, was demonstrated to be a potential intermediate in the catalytic cycle. Furthermore, the reductive elimination event was probed with ^(18)O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.

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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: August 29, 2014; Revised: September 17, 2014. Article first published online: 6 NOV 2014. We gratefully acknowledge financial support from the King Abdullah University of Science and Technology Centre in Development, King Fahd University of Petroleum and Minerals, the NSF, and the Gordon and Betty Moore Foundation. P.E.G. is grateful to the NIH for a postdoctoral fellowship.

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Supplemental Material - anie_201408650_sm_miscellaneous_information.pdf

Accepted Version - nihms-647073.pdf

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