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. 2008 Nov 21;6(22):4083-8.
doi: 10.1039/b813246a. Epub 2008 Oct 9.

Mechanistic approaches to palladium-catalyzed alkene difunctionalization reactions

Katrina H Jensen  1 , Matthew S Sigman
Affiliations

Mechanistic approaches to palladium-catalyzed alkene difunctionalization reactions

Katrina H Jensen et al. Org Biomol Chem. .

Abstract

Alkene difunctionalization, the addition of two functional groups across a double bond, exemplifies a class of reactions with significant synthetic potential. This emerging area examines recent developments of palladium-catalyzed difunctionalization reactions, with a focus on mechanistic strategies that allow for functionalization of a common palladium alkyl intermediate.

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Figures

Fig. 1
Fig. 1
Mechanistic possibilities for Pd-alkyl intermediates.
Fig. 2
Fig. 2
Pd-catalyzed diamination of terminal dienes.
Fig. 3
Fig. 3
Pd-catalyzed asymmetric diamination of dienes and alkenes.
Fig. 4
Fig. 4
Pd-catalyzed difunctionalizations involving oxypalladation–alkene insertion.
Fig. 5
Fig. 5
Pd-catalyzed difunctionalization reactions involving aminopalladation–alkene insertion.
Fig. 6
Fig. 6
Pd-catalyzed dioxygenation of o-vinylphenols.
Fig. 7
Fig. 7
Asymmetric dialkoxylation of o-vinyl phenols.
Fig. 8
Fig. 8
Intramolecular Pd-catalyzed difunctionalization reactions.
Fig. 9
Fig. 9
Mechanistic experiments supporting syn-aminopalladation and SN2-type substitution.
Fig. 10
Fig. 10
Pd-catalyzed aminoacetoxylation of alkenes and mechanistic experiments.
Fig. 11
Fig. 11
Pd-catalyzed aminooxygenation of alkenes and mechanistic experiments.
Fig. 12
Fig. 12
Pd-catalyzed cyclopropanation of enynes.
Fig. 13
Fig. 13
Pd-catalyzed dioxygenation of alkenes.
Scheme 1
Scheme 1
Proposed mechanism for Pd-catalyzed diene difunctionalization.
Scheme 2
Scheme 2
Proposed mechanism for Pd-catalyzed diene difunctionalization reaction with diaziridinones.
Scheme 3
Scheme 3
Proposed mechanism for Pd-catalyzed difunctionalization reactions involving nucleopalladation–alkene insertion.
Scheme 4
Scheme 4
Proposed mechanism for Pd-catalyzed dihydroxylation or hydroxyalkoxylation of o-vinyl phenols.
Scheme 5
Scheme 5
Proposed mechanism for Pd-catalyzed dialkoxylation of o-vinyl phenols.
Scheme 6
Scheme 6
Proposed mechanism for Pd-catalyzed difunctionalization involving PdII–PdIV oxidation.
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References

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