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      A Cooperative Hydrogen Bond Donor-Brønsted Acid System for the Enantioselective Synthesis of Tetrahydropyrans

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          Abstract

          <p class="first" id="P1">Carbocations stabilized by adjacent oxygen atoms are useful reactive intermediates involved in fundamental chemical transformations. These oxocarbenium ions typically lack sufficient electron density to engage established chiral Brønsted or Lewis acid catalysts, presenting a major challenge to their widespread application in asymmetric catalysis. Leading methods for selectivity operate primarily through electrostatic pairing between the oxocarbenium ion and a chiral counterion. A general approach to new enantioselective transformations of oxocarbenium ions requires novel strategies that address the weak binding capabilities of these intermediates. We demonstrate herein a novel cooperative catalysis system for selective reactions with oxocarbenium ions. This new strategy has been applied to a highly selective and rapid <i>oxa</i>-Pictet-Spengler reaction and highlights a powerful combination of an achiral hydrogen bond donor with a chiral Brønsted acid. </p><p id="P2">A novel, cooperative catalytic method for the asymmetric <i>oxa</i>-Pictet-Spengler reaction has been developed. This method, demonstrated in the synthesis of substituted tetrahydropyranoindoles, has enabled a six-step asymmetric synthesis of (−)-coixspirolactam C. </p><p id="P3"> <div class="figure-container so-text-align-c"> <img alt="" class="figure" src="/document_file/a34b4861-60a3-40c9-9410-bcf92764af90/PubMedCentral/image/nihms-1521654-f0001.jpg"/> </div> </p>

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          Most cited references 54

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          Pyrrolidinyl-spirooxindole natural products as inspirations for the development of potential therapeutic agents.

          The 3,3'-pyrrolidinyl-spirooxindole unit is a privileged heterocyclic motif that forms the core of a large family of alkaloid natural products with strong bioactivity profiles and interesting structural properties. Significant recent advances in the synthesis of this fused heterocyclic system have led to intense interest in the development of related compounds as potential medicinal agents or biological probes.
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            Complete field guide to asymmetric BINOL-phosphate derived Brønsted acid and metal catalysis: history and classification by mode of activation; Brønsted acidity, hydrogen bonding, ion pairing, and metal phosphates.

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              Catalytic enantioselective addition to imines.

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                Author and article information

                Journal
                Angewandte Chemie International Edition
                Angew. Chem. Int. Ed.
                Wiley
                14337851
                December 21 2018
                December 21 2018
                November 27 2018
                : 57
                : 52
                : 17225-17229
                Affiliations
                [1 ]Department of Chemistry; Center for Molecular Innovation and Drug Discovery; Northwestern University; Silverman Hall Evanston IL 60208 USA
                Article
                10.1002/anie.201811383
                6419772
                30380196
                © 2018

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