Asymmetric Synthesis of Allenyl Oxindoles and Spirooxindoles by a Catalytic Enantioselective Saucy–Marbet Claisen Rearrangement

Authors

  • Trung Cao,

    1. Department of Chemistry, Penn Merck High Throughput Experimentation Laboratory, University of Pennsylvania, Philadelphia, PA 19104-6323 (USA)
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  • Joshua Deitch,

    1. Department of Chemistry, Penn Merck High Throughput Experimentation Laboratory, University of Pennsylvania, Philadelphia, PA 19104-6323 (USA)
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  • Dr. Elizabeth C. Linton,

    1. Department of Chemistry, Penn Merck High Throughput Experimentation Laboratory, University of Pennsylvania, Philadelphia, PA 19104-6323 (USA)
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  • Prof. Marisa C. Kozlowski

    Corresponding author
    1. Department of Chemistry, Penn Merck High Throughput Experimentation Laboratory, University of Pennsylvania, Philadelphia, PA 19104-6323 (USA)
    • Department of Chemistry, Penn Merck High Throughput Experimentation Laboratory, University of Pennsylvania, Philadelphia, PA 19104-6323 (USA)
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  • Financial support was provided by the NSF (CHE-0911713) and NIH (RO1GM087605). Partial instrumentation support was provided by the NIH for MS (1S10RR023444) and NMR (1S10RR022442) and by the NSF for an X-ray diffractometer (CHE-0840438). The invaluable assistance of Dr. Patrick Carroll in obtaining the crystal structures is gratefully acknowledged.

Abstract

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Saucy selection: The first catalytic, enantioselective Saucy–Marbet Claisen rearrangement has been achieved. Palladium(II) (R)-binap or tBuphox catalysts L*Pd(SbF6)2 were employed to generate allenyl oxindoles or spirolactones bearing a quaternary center with up to 98 % ee.

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