Journal
HELVETICA CHIMICA ACTA
Volume 95, Issue 10, Pages 1985-2006Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/hlca.201200412
Keywords
Enantioselective synthesis; Aldehydes; a-substituted a; ss-unsaturated; Organocatalysis; Dienamine activation; Secondary amine; Alkylation; X-Ray crystallography
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Funding
- ICIQ Foundation
- MICINN [CTQ2010-15513]
- European Research Council (ERC Starting Grant ORGA-NAUT)
- MICINN
- ICREA Funding Source: Custom
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The direct and enantioselective ?-alkylation of a-substituted a,beta-unsaturated aldehydes proceeding under dienamine catalysis is described. We have found that the Seebach modification of the diphenyl-prolinol silyl ether catalyst in combination with saccharin as an acidic additive promotes an SN1 alkylation pathway, while ensuring complete ?-site selectivity and a high stereocontrol. Theoretical and spectroscopic investigations have provided insights into the conformational behavior of the covalent dienamine intermediate derived from the condensation of 2-methylpent-2-enal and the chiral amine. Implications for the mechanism of stereoinduction are discussed.
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