Asymmetric Palladium-Catalyzed Allylic Alkylation Using Dialkylzinc Reagents: A Remarkable Ligand Effect

A serendipitously discovered palladium‐catalyzed asymmetric allylic alkylation reaction with diorganozinc reagents, which displays broad functional group compatibility, is reported. This novel transformation hinges on a remarkable ligand effect which overrides the standard “umpolung” reactivity of a...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-07, Vol.53 (27), p.7068-7073
Main Authors: Misale, Antonio, Niyomchon, Supaporn, Luparia, Marco, Maulide, Nuno
Format: Article
Language:English
Subjects:
Alkylation
Asymmetry
Compatibility
deracemization
diethylzinc
Displays
enantioselectivity
Functional groups
Hinges
Ligands
palladium
Transformations
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Summary:A serendipitously discovered palladium‐catalyzed asymmetric allylic alkylation reaction with diorganozinc reagents, which displays broad functional group compatibility, is reported. This novel transformation hinges on a remarkable ligand effect which overrides the standard “umpolung” reactivity of allyl–palladium intermediates in the presence of dialkylzincs. Owing to its mild conditions, enantioselective allylic alkylations of racemic allylic electrophiles are possible in the presence of sensitive functional groups. Umpole‐me‐not: A serendipitously discovered palladium‐catalyzed asymmetric allylic alkylation reaction with diorganozinc reagents displays broad functional group compatibility. This novel transformation hinges on a remarkable ligand effect which overrides the standard “umpolung” reactivity of allyl–palladium intermediates in the presence of dialkylzinc compounds.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201309074