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Formation of Contiguous Quaternary and Tertiary Stereocenters by Sequential Asymmetric Conjugate Addition of Grignard Reagents to 2-Substituted Enones and Mg-Enolate Trapping

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Published in Chemistry - A European Journal. 2015, vol. 21, no. 23, p. 8597-8606
Abstract Herein a comprehensive study is provided on the asymmetric conjugate addition (ACA) of Grignard reagents to α-substituted cyclic enones. After the elucidation of the optimal experimental conditions, the scope of Grignard reagents and Michael acceptors was examined. Whereas secondary Grignards gave better enantioselectivities with 2-cyclopentenones, both linear and branched Grignard reagents were tolerated for the ACA to 2-methylcyclohexenone. The sequential ACA–enolate trapping, which leads to quaternary stereocenters, was then studied. Thus, many electrophiles have been tested, thereby giving rise to highly functionalized cyclic ketones with contiguous α-quaternary and β-tertiary centers. The present technique is believed to bring a new approach to versatile terpenoid-like skeletons of bioactive natural products. Straightforward derivatizations of enantioenriched saturated cyclic ketones further support the potential of the present methodology in synthesis.
Keywords AdditionCopperEnantioselectivityGrignard reagentsNatural products
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Other version: http://doi.wiley.com/10.1002/chem.201500292
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GERMAIN, Nicolas, ALEXAKIS, Alexandre. Formation of Contiguous Quaternary and Tertiary Stereocenters by Sequential Asymmetric Conjugate Addition of Grignard Reagents to 2-Substituted Enones and Mg-Enolate Trapping. In: Chemistry - A European Journal, 2015, vol. 21, n° 23, p. 8597-8606. https://archive-ouverte.unige.ch/unige:72891

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Deposited on : 2015-06-01

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