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. 2009;48(17):3146-9.
doi: 10.1002/anie.200900218.

Palladium-catalyzed oxidative intermolecular difunctionalization of terminal alkenes with organostannanes and molecular oxygen

Kaveri Balan Urkalan  1 , Matthew S Sigman
Affiliations

Palladium-catalyzed oxidative intermolecular difunctionalization of terminal alkenes with organostannanes and molecular oxygen

Kaveri Balan Urkalan et al. Angew Chem Int Ed Engl. 2009.

Abstract

A cationic palladium complex catalyzes the title transformations, which are thought to proceed via a pi-allyl or pi-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 beta-hydride elimination and transmetalation. DMA=dimethylacetamide, Tf=triflyl.

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Figures

Scheme 1
Scheme 1
Proposed mechanism for the oxidative Heck reaction (a) and interception of the σ-alkyl palladium(II) intermediate by transmetalation (b).
Figure 1
Figure 1
1,2-Diarylation versus 1,1-diarylation of styrenes and resulting Hammett analysis.
Scheme 2
Scheme 2
1,1-Diarylation of terminal alkenes (a) and related mechanistic experiments (b).
See this image and copyright information in PMC

References

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