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Aumann, Rudolf

Organische Synthesen mit übergangsmetall‐Komplexen, 66. 2‐Aminopyrrole durch Metathese von (β‐Aminovinyl)carben‐Chrom‐ und ‐Wolfram‐Komplexen mit Isocyaniden

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  • Media type: E-Article
  • Title: Organische Synthesen mit übergangsmetall‐Komplexen, 66. 2‐Aminopyrrole durch Metathese von (β‐Aminovinyl)carben‐Chrom‐ und ‐Wolfram‐Komplexen mit Isocyaniden
  • Contributor: Aumann, Rudolf
  • imprint: Wiley, 1993
  • Published in: Chemische Berichte
  • Language: English
  • DOI: 10.1002/cber.19931261022
  • ISSN: 0009-2940
  • Keywords: Inorganic Chemistry
  • Origination:
  • Footnote:
  • Description: <jats:p><jats:bold>Organic Syntheses via Transition Metal Complexes, 66<jats:sup>[1]</jats:sup>. — 2‐Aminopyrroles by Metathesis of (β‐Aminovinyl)carbene Complexes of Chromium and Tungsten with Isocyanides</jats:bold></jats:p><jats:p>(β‐Aminovinyl)carbene complexes L<jats:sub><jats:italic>n</jats:italic></jats:sub>MC(OEt)—CHC(Ph)‐NHR (<jats:italic>Z</jats:italic>)‐<jats:bold>3a—d</jats:bold> [L<jats:sub><jats:italic>n</jats:italic></jats:sub>M = (CO)<jats:sub>5</jats:sub>Cr, (CO)<jats:sub>5</jats:sub>W; R = Ph, <jats:italic>i</jats:italic>Pr, CH<jats:sub>2</jats:sub>Ph] react with two equivalents of isocyanides R<jats:sup>1</jats:sup>—NC <jats:bold>5</jats:bold> (R = <jats:italic>c</jats:italic>‐C<jats:sub>6</jats:sub>H<jats:sub>11</jats:sub>, <jats:italic>t</jats:italic>‐C<jats:sub>4</jats:sub>H<jats:sub>9</jats:sub>) to give 2‐amino‐3‐ethoxypyrroles <jats:bold>7a—e</jats:bold> and isocyanide complexes L<jats:sub><jats:italic>n</jats:italic></jats:sub>M(R<jats:sup>1</jats:sup>—NC) <jats:bold>6</jats:bold>. The reaction involves the formation of ketenimine complexes by metathesis. These are key intermediates. The pyrroles <jats:bold>7</jats:bold> are easily oxidized by air to give amidines PhN(R<jats:sup>1</jats:sup>NH)C—C(OEt)CH—COPh <jats:bold>9</jats:bold> (R = <jats:italic>c</jats:italic>‐C<jats:sub>6</jats:sub>H<jats:sub>11</jats:sub>, <jats:italic>t</jats:italic>‐C<jats:sub>4</jats:sub>H<jats:sub>9</jats:sub>). <jats:bold>7a</jats:bold> forms a Michael adduct <jats:bold>10a</jats:bold> as well as a Diels‐Alder adduct <jats:bold>11a</jats:bold> with <jats:italic>N</jats:italic>‐phenylmaleimide. A 1‐amino‐2‐ethoxybenzene <jats:bold>12a</jats:bold> is obtained from <jats:bold>11a</jats:bold> by elimination of aniline.</jats:p>