• Media type: E-Article
  • Title: Synthesis of Aristotelia‐Type Alkaloids. Part VIBiomimetic Synthesis of (+)‐Aristofruticosine
  • Contributor: Beerli, René; Borschberg, Hans‐Jürg
  • Published: Wiley, 1991
  • Published in: Helvetica Chimica Acta
  • Extent: 110-116
  • Language: English
  • DOI: 10.1002/hlca.19910740113
  • ISSN: 0018-019X; 1522-2675
  • Keywords: Inorganic Chemistry ; Organic Chemistry ; Physical and Theoretical Chemistry ; Drug Discovery ; Biochemistry ; Catalysis
  • Abstract: <jats:title>Abstract</jats:title><jats:p>(<jats:italic>S</jats:italic>)‐Perilla alcohol (<jats:bold>5</jats:bold>) was transformed into (<jats:italic>S</jats:italic>)‐7‐(phenylthio)‐<jats:italic>p</jats:italic>‐menth‐1‐en‐8‐amine (<jats:bold>11</jats:bold>) in five steps. Condensation of this building block with 1‐(4‐methoxyphenylsulfonyl)‐1<jats:italic>H</jats:italic>‐indole‐3‐acetaldehyde (<jats:bold>12</jats:bold>) led to the expected imine <jats:bold>15</jats:bold> which cyclized in 54% yield to protected 20‐(phenylthio)hobartine <jats:bold>16</jats:bold> upon exposure to anh. HCOOH. Treatment of this intermediate with an alkylating reagent led to (+)‐aristofruticosine protected in the indole moiety <jats:italic>via</jats:italic> an intramolecular, allylic nucleophilic displacement reaction. Subsequent reductive removal of the protecting group completed the first synthesis of the <jats:italic>Aristotelia</jats:italic> alkaloid (+)‐aristofruticosine ((+)‐<jats:bold>4</jats:bold>). This straightforward synthesis confirmed the tentative structure (+)‐<jats:bold>4</jats:bold>, proposed by <jats:italic>Bick</jats:italic> and <jats:italic>Hai</jats:italic>, and established the hitherto unknown absolute configuration of this metabolite.</jats:p>
  • Description: <jats:title>Abstract</jats:title><jats:p>(<jats:italic>S</jats:italic>)‐Perilla alcohol (<jats:bold>5</jats:bold>) was transformed into (<jats:italic>S</jats:italic>)‐7‐(phenylthio)‐<jats:italic>p</jats:italic>‐menth‐1‐en‐8‐amine (<jats:bold>11</jats:bold>) in five steps. Condensation of this building block with 1‐(4‐methoxyphenylsulfonyl)‐1<jats:italic>H</jats:italic>‐indole‐3‐acetaldehyde (<jats:bold>12</jats:bold>) led to the expected imine <jats:bold>15</jats:bold> which cyclized in 54% yield to protected 20‐(phenylthio)hobartine <jats:bold>16</jats:bold> upon exposure to anh. HCOOH. Treatment of this intermediate with an alkylating reagent led to (+)‐aristofruticosine protected in the indole moiety <jats:italic>via</jats:italic> an intramolecular, allylic nucleophilic displacement reaction. Subsequent reductive removal of the protecting group completed the first synthesis of the <jats:italic>Aristotelia</jats:italic> alkaloid (+)‐aristofruticosine ((+)‐<jats:bold>4</jats:bold>). This straightforward synthesis confirmed the tentative structure (+)‐<jats:bold>4</jats:bold>, proposed by <jats:italic>Bick</jats:italic> and <jats:italic>Hai</jats:italic>, and established the hitherto unknown absolute configuration of this metabolite.</jats:p>
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