One-Pot Organocatalytic Domino Michael/α-Alkylation Reactions: Direct Catalytic Enantioselective Cyclopropanation and Cyclopentanation Reactions

Authors

  • Ismail Ibrahem Dr.,

    1. Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154-908
    2. Berzelii Center EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden)
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  • Gui-Ling Zhao Dr.,

    1. Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154-908
    2. Berzelii Center EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden)
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  • Ramon Rios Dr.,

    1. Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154-908
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  • Jan Vesely Dr.,

    1. Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154-908
    2. Berzelii Center EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden)
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  • Henrik Sundén Dr.,

    1. Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154-908
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  • Pawel Dziedzic,

    1. Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154-908
    2. Berzelii Center EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden)
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  • Armando Córdova Prof. Dr.

    1. Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154-908
    2. Berzelii Center EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden)
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Abstract

The development of one-pot organocatalytic domino Michael/α-alkylation reactions between bromomalonates or bromoacetoacetate esters and α,β-unsaturated aldehydes is presented. The chiral-amine-catalyzed reactions with bromomalonates as substrates give access to the corresponding 2-formylcyclopropane derivatives in high yields with excellent diastereoselectivity and up to 99 % ee. The catalytic domino Michael/α-alkylation reactions between 4-bromo-acetoacetate and enals provide a route for the synthesis of functionalized cyclopentanones in good to high yields with 93–99 % ee. The products from the organocatalytic reactions were also reduced with high diastereoselectivity to the corresponding cyclopropanols and cyclopentanols, respectively. Moreover, one-pot combinations of amine and heterocyclic carbene catalysis (AHCC) enabled the highly enantioselective synthesis of β-malonate esters (91–97 % ee) from the reaction between bromomalonates and enals. The tandem catalysis included the catalytic domino reaction followed by catalytic in situ chemoselective ring-opening of the 2-formylcyclopropane intermediates.

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