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Palladium-Catalyzed Oxidative Wacker Cyclizations in Nonpolar Organic Solvents with Molecular Oxygen: A Stepping Stone to Asymmetric Aerobic Cyclizations

Authors

  • Raissa M. Trend,

    1. The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 164-30, Pasadena, CA 91125, USA, Fax: (+1) 626–564–9297
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  • Yeeman K. Ramtohul Dr.,

    1. The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 164-30, Pasadena, CA 91125, USA, Fax: (+1) 626–564–9297
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  • Eric M. Ferreira,

    1. The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 164-30, Pasadena, CA 91125, USA, Fax: (+1) 626–564–9297
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  • Brian M. Stoltz Prof.

    1. The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 164-30, Pasadena, CA 91125, USA, Fax: (+1) 626–564–9297
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  • The authors wish to thank the NIH-NIGMS (R01 GM65961-01), the University of California TRDRP (postdoctoral fellowship to YKR), the NSF (predoctoral fellowship to EMF), the Dreyfus Foundation, Merck Research Laboratories, Research Corporation, and Abbott Laboratories for generous financial support. Dr. Richmond Sarpong and Mr. Julius Su are gratefully acknowledged for molecular modeling assistance.

Abstract

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A variety of Pd-catalyzed oxidative nucleophile/alkene cyclizations proceeds in excellent yield under simple aerobic conditions in nonpolar media (Pd catalyst, pyridine, and O2 in toluene). Nucleophiles for these cyclizations include phenols, carboxylic acids, amides, and primary alcohols. Additionally, enantioselective catalysis is feasible with a Pd-sparteine system (see picture). Enantioselectivities of up to 90 % ee are observed for simple phenol/alkene cyclizations.

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