Total Syntheses of Echitamine, Akuammiline, Rhazicine, and Pseudoakuammigine

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  • Xiang Zhang
    State Key Laboratory of Bioorganic and Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
  • Badrinath N. Kakde
    State Key Laboratory of Bioorganic and Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
  • Rui Guo
    State Key Laboratory of Bioorganic and Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
  • Sonyabapu Yadav
    State Key Laboratory of Bioorganic and Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
  • Yucheng Gu
    Syngenta Jealott's Hill International Research Centre Bracknell Berkshire RG42 6EY UK
  • Ang Li
    State Key Laboratory of Bioorganic and Natural Products Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China

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<jats:title>Abstract</jats:title><jats:p>Echitamine (<jats:bold>1</jats:bold>) and akuammiline (<jats:bold>2</jats:bold>) are representative members of a fascinating class of monoterpenoid indole alkaloids. We report the syntheses of <jats:bold>2</jats:bold> and its congener deacetylakuammiline (<jats:bold>3</jats:bold>). The azabicyclo[3.3.1]nonane motif was assembled through silver‐catalyzed internal alkyne cyclization, and one‐pot C−O bond cleavage/C−N bond formation furnished the pentacyclic scaffold. Compound <jats:bold>3</jats:bold> then served as a common intermediate for preparing a series of structurally diverse and synthetically challenging congeners including <jats:bold>1</jats:bold>. A position‐selective Polonovski–Potier reaction followed by formal N‐4 migration built the core of <jats:italic>N</jats:italic>‐demethylechitamine (<jats:bold>4</jats:bold>) and <jats:bold>1</jats:bold>. An alternative route featuring Meisenheimer rearrangement gave <jats:bold>4</jats:bold> as well. Oxidation of the alcohol within <jats:bold>3</jats:bold> gave rhazimal (<jats:bold>5</jats:bold>), which underwent tandem indolenine hydrolysis, hemiaminalization, and hemiketalization to form rhazicine (<jats:bold>6</jats:bold>). A sequence of N,O‐ketalization and reductive amination secured the chemoselectivity of N‐methylation, leading to pseudoakuammigine (<jats:bold>7</jats:bold>).</jats:p>

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