Preparation of poly[(3<i>S</i>)‐1,2,3,4‐tetrahydroisoquinoline‐2,3‐diylmethylene] and its use as chiral catalyst in the addition of arenethiols to 2‐cyclohexen‐1‐one

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<jats:title>Abstract</jats:title><jats:p>Poly[(3<jats:italic>S</jats:italic>)‐1,2,3,4‐tetrahydroisoquinoline‐2,3‐diylmethylene] (<jats:bold>4</jats:bold>) and (3<jats:italic>S</jats:italic>)‐3‐(1,2,3,4‐tetrahydroisoquinolin‐2‐ylmethyl)‐2‐methyl‐1,2,3,4‐tetrahydroisoquinoline (<jats:bold>7</jats:bold>) were prepared using (3<jats:italic>S</jats:italic>)‐1,2,3,4‐tetrahydro‐3‐isoquinolinecarboxylic acid (<jats:bold>1</jats:bold>) as starting material. The optically active amines <jats:bold>4</jats:bold> and <jats:bold>7</jats:bold> were used as asymmetric catalysts for the addition of thiophenol (<jats:bold>8a</jats:bold>), 4‐<jats:italic>tert</jats:italic>‐butylthiophenol (<jats:bold>8b</jats:bold>), or 4‐chlorothiophenol (<jats:bold>8c</jats:bold>) to 2‐cyclohexen‐1‐one (<jats:bold>9</jats:bold>). <jats:bold>4</jats:bold> yielded 3‐phenylthiocyclohexanone (<jats:bold>10a</jats:bold>) with the highest optical yield of 24% at −25°C, showing a marked polymer effect with respect to enantiomeric excess.</jats:p>

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