Potentially Biomimetic Total Synthesis and Relative Stereochemical Assignment of (±)-Gracilamine

Authors

  • Songchuan Tian,

    1. State Key Laboratory of Bioorganic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032 (P.R. China)
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  • Dr. Weiwei Zi,

    1. State Key Laboratory of Bioorganic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032 (P.R. China)
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  • Prof. Dr. Dawei Ma

    Corresponding author
    1. State Key Laboratory of Bioorganic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032 (P.R. China)
    • State Key Laboratory of Bioorganic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032 (P.R. China)
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  • The authors are grateful to the National Basic Research Program of China (973 Program, grant 2010CB833200) and the Chinese Academy of Sciences and the National Natural Science Foundation of China (grants 21132008 and 20921091) for their financial support.

Abstract

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Gracil(e): The total synthesis of gracilamine features a potentially biomimetic intramolecular [3+2] cycloaddition to assemble its two fused five-membered rings and a debenzylation/ring-opening reaction to obtain the aldehyde intermediate (see scheme). The success of this synthesis provides a circumstantial evidence that supports the biosynthesis pathway of gracilamine proposed previously.

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