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Mechanistic Duality in Tertiary Amine Additions to Thermally Generated Hexadehydro-Diels-Alder Benzynes.

ABSTRACT: Reported here are studies directed at understanding the mechanism of tertiary amine addition to hexadehydro-Diels-Alder (HDDA)-generated benzynes. Tertiary amines are presumed to engage benzynes by generation of a zwitterionic intermediate. Simple trialkylamines undergo intermolecular protonation by a protic nucleophile to give an aryl ammonium intermediate that is then dealkylated. Amines containing acidified ?-protons undergo an intramolecular elimination to give the aniline and an alkene. Finally, amino alcohols react at either of their N- or O atoms, depending upon the extent of internal hydrogen bonding.

SUBMITTER: Ross SP

PROVIDER: S-EPMC5650509 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

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Mechanistic Duality in Tertiary Amine Additions to Thermally Generated Hexadehydro-Diels-Alder Benzynes.

Ross Sean P SP Baire Beeraiah B Hoye Thomas R TR

Organic letters 20171005 20

Reported here are studies directed at understanding the mechanism of tertiary amine addition to hexadehydro-Diels-Alder (HDDA)-generated benzynes. Tertiary amines are presumed to engage benzynes by generation of a zwitterionic intermediate. Simple trialkylamines undergo intermolecular protonation by a protic nucleophile to give an aryl ammonium intermediate that is then dealkylated. Amines containing acidified β-protons undergo an intramolecular elimination to give the aniline and an alkene. Fin ...[more]

PMID: 28981290

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