Aerobic Palladium-Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite

Zachary K. Wickens; Pablo E. Guzman; Robert H. Grubbs

doi:10.1002/anie.201408650

Aerobic Palladium-Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite

Zachary K. Wickens, Pablo E. Guzman, Robert H. Grubbs

Research output: Contribution to journal › Article › peer-review

42 Scopus citations

Abstract

Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. Avariety 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 18O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.

Original language	English (US)
Pages (from-to)	236-240
Number of pages	5
Journal	ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume	54
Issue number	1
DOIs	https://doi.org/10.1002/anie.201408650
State	Published - 2015
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2021-10-08
Acknowledgements: 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 (CHE 1212767), NIH (R01GM031332), and the Gordon and Betty Moore Foundation. P.E.G. is grateful to the NIH for a postdoctoral fellowship.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

General Chemistry
Catalysis

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10.1002/anie.201408650

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title = "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. Avariety 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 18O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.",

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AU - Guzman, Pablo E.

AU - Grubbs, Robert H.

N1 - KAUST Repository Item: Exported on 2021-10-08 Acknowledgements: 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 (CHE 1212767), NIH (R01GM031332), and the Gordon and Betty Moore Foundation. P.E.G. is grateful to the NIH for a postdoctoral fellowship. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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N2 - Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. Avariety 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 18O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.

AB - Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. Avariety 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 18O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.

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Aerobic Palladium-Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite

Abstract

Bibliographical note

ASJC Scopus subject areas

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