The Cinchona Primary Amine-Catalyzed Asymmetric Epoxidation and 
Hydroperoxidation of α,β-Unsaturated Carbonyl Compounds with Hydrogen Peroxide

Lifchits, Olga; Mahlau, Manuel; Reisinger, Corinna M.; Lee, Anna; Farès, Christophe; Polyak, Iakov; Gopakumar, Gopinadhanpillai; Thiel, Walter; List, Benjamin

doi:10.1021/ja402058v

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The Cinchona Primary Amine-Catalyzed Asymmetric Epoxidation and Hydroperoxidation of α,β-Unsaturated Carbonyl Compounds with Hydrogen Peroxide

MPS-Authors

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Lifchits, Olga
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58786

Mahlau, Manuel
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58922

Reisinger, Corinna M.
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58741

Lee, Anna
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58537

Farès, Christophe
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58894

Polyak, Iakov
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58583

Gopakumar, Gopinadhanpillai
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons59045

Thiel, Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58764

List, Benjamin
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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ja402058v_si_001.pdf
(Supplementary material), 8MB

ja402058v_si_002.pdf
(Supplementary material), 165KB

Citation

Lifchits, O., Mahlau, M., Reisinger, C. M., Lee, A., Farès, C., Polyak, I., et al. (2013). The Cinchona Primary Amine-Catalyzed Asymmetric Epoxidation and Hydroperoxidation of α,β-Unsaturated Carbonyl Compounds with Hydrogen Peroxide. Journal of the American Chemical Society, 135(17), 6677-6693. doi:10.1021/ja402058v.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0014-A36C-0

Abstract

Using cinchona alkaloid-derived primary amines as catalysts and aqueous hydrogen peroxide as the oxidant, we have developed highly enantioselective Weitz–Scheffer-type epoxidation and hydroperoxidation reactions of α,β-unsaturated carbonyl compounds (up to 99.5:0.5 er). In this article, we present our full studies on this family of reactions, employing acyclic enones, 5–15-membered cyclic enones, and α-branched enals as substrates. In addition to an expanded scope, synthetic applications of the products are presented. We also report detailed mechanistic investigations of the catalytic intermediates, structure–activity relationships of the cinchona amine catalyst, and rationalization of the absolute stereoselectivity by NMR spectroscopic studies and DFT calculations.