Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 11, Issue 1, Pages 174-184Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200400666
Keywords
allylation; asymmetric catalysis; asymmetric synthesis; palladium; quaternary stereocenters
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Funding
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R37GM013598, R01GM013598] Funding Source: NIH RePORTER
- NIGMS NIH HHS [GM-13598] Funding Source: Medline
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Palladium-catalyzed asymmetric allylic alkylation of nonstabilized ketone enolates to generate quaternary centers has been achieved in excellent yield and enantioselectivity. Optimized conditions consist of performing the reaction in the presence of two equivalents of LDA as base, one equivalent of trimethytin chloride as a Lewis acid, 1,2-dimethoxyethane as the solvent, and a catalytic amount of a chiral palladium complex formed from pi-allyl palladium chloride dimer 3 and cyclohexyldiamine derived chiral ligand 4. Linearly substituted, acyclic 1,3-dialkyl substituted, and unsubstituted allylic carbonates function well as electrophiles. A variety of alpha-tetralones, cyclohexanones, and cyclopentanones can be employed as nucleophiles. The absolute configuration generated is consistent with the current model in which steric factors control stereofacial differentiation. The quaternary substituted products available by this method are versatile substrates for further elaboration.
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