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>