Research support from the ICIQ Foundation, MICINN (grant CTQ2010-15513), and the European Research Council (ERC Starting grant agreement no. 278541—ORGA-NAUT) is gratefully acknowledged. Y.L. is grateful to the European Union for a Marie Curie fellowship (grant FP7-PEOPLE-2010-IIF no. 273088). The authors thank Eduardo Escudero-Adán for X-ray crystallographic analysis.
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Communication
Aminocatalytic Enantioselective 1,6 Additions of Alkyl Thiols to Cyclic Dienones: Vinylogous Iminium Ion Activation †
Article first published online: 22 MAY 2012
DOI: 10.1002/anie.201202392
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Tian, X., Liu, Y. and Melchiorre, P. (2012), Aminocatalytic Enantioselective 1,6 Additions of Alkyl Thiols to Cyclic Dienones: Vinylogous Iminium Ion Activation . Angew. Chem. Int. Ed., 51: 6439–6442. doi: 10.1002/anie.201202392
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Publication History
- Issue published online: 21 JUN 2012
- Article first published online: 22 MAY 2012
- Manuscript Received: 27 MAR 2012
Funded by
- ICIQ Foundation
- MICINN. Grant Number: CTQ2010-15513
- European Research Council. Grant Number: 278541—ORGA-NAUT
Keywords:
- asymmetric synthesis;
- iminium ions;
- nucleophilic addition;
- organocatalysis;
- vinylogous reactivity
Remote transmission: In the presence of chiral amines, 2,4-dienones are activated toward the attack of a nucleophile at the δ position, a mode of activation that is termed vinylogous iminium ion catalysis. Specifically, the 1,6 addition of alkyl thiols to β-substituted cyclic dienones was catalyzed by a cinchona-based primary amine; the reaction was highly stereoselective and displayed high selectivity for reaction at the δ position.