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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.

SUBMITTER: Wickens ZK

PROVIDER: S-EPMC4285779 | biostudies-literature | 2015 Jan

REPOSITORIES: biostudies-literature

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Aerobic palladium-catalyzed dioxygenation of alkenes enabled by catalytic nitrite.

Wickens Zachary K ZK Guzmán Pablo E PE Grubbs Robert H RH

Angewandte Chemie (International ed. in English) 20141106 1

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 reduc ...[more]

PMID: 25376666

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