This research was supported by the National Institutes of Health (NIGMS RO1 GM3540). M.S.S. thanks the Dreyfus Foundation (Teacher-Scholar Award) and Pfizer for their support. We are grateful to Johnson Matthey for the gift of various palladium salts. We thank Keith Gligorich for initial experiments.
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Communication
Palladium-Catalyzed Oxidative Intermolecular Difunctionalization of Terminal Alkenes with Organostannanes and Molecular Oxygen†
Article first published online: 23 MAR 2009
DOI: 10.1002/anie.200900218
Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Urkalan, K. and Sigman, M. (2009), Palladium-Catalyzed Oxidative Intermolecular Difunctionalization of Terminal Alkenes with Organostannanes and Molecular Oxygen. Angewandte Chemie International Edition, 48: 3146–3149. doi: 10.1002/anie.200900218
- †
Publication History
- Issue published online: 7 APR 2009
- Article first published online: 23 MAR 2009
- Manuscript Received: 14 JAN 2009
Funded by
- National Institutes of Health. Grant Number: NIGMS RO1 GM3540
- Dreyfus Foundation
- Pfizer
Keywords:
- cross-coupling;
- homogeneous catalysis;
- molecular oxygen;
- palladium;
- reaction mechanisms
Graphical Abstract
A cationic palladium complex catalyzes the title transformations, which are thought to proceed via a π-allyl or π-benzyl intermediate. The regioselectivity of the reaction (1,2- or 1,1-difunctionalization) depends on the type of terminal double bond (conjugated or nonconjugated) in the substrate (see scheme) and appears to be controlled by the relative rates of β-hydride elimination and transmetalation. DMA=dimethylacetamide, Tf=triflyl.
Abstract
A cationic palladium complex catalyzes the title transformations, which are thought to proceed via a π-allyl or π-benzyl intermediate. The regioselectivity of the reaction (1,2- or 1,1-difunctionalization) depends on the type of terminal double bond (conjugated or nonconjugated) in the substrate (see scheme) and appears to be controlled by the relative rates of β-hydride elimination and transmetalation. DMA=dimethylacetamide, Tf=triflyl.