The Phenol-Ene Reaction: Biaryl Synthesis via Trapping Reactions between HDDA-Generated Benzynes and Phenolics

Juntian Zhang; Dawen Niu; Vincent A. Brinker; Thomas R. Hoye

doi:10.1021/acs.orglett.6b02830

The Phenol-Ene Reaction: Biaryl Synthesis via Trapping Reactions between HDDA-Generated Benzynes and Phenolics

Juntian Zhang, Dawen Niu, Vincent A. Brinker, Thomas R. Hoye

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

Benzynes produced thermally by the cycloisomerization of triyne-containing precursors [i.e., by the hexadehydro-Diels-Alder (HDDA) reaction] react with phenols at the carbon ortho to the hydroxyl in an enelike fashion. Following tautomerization of the intermediate cyclohexadienones, this produces biaryl derivatives. DFT calculations of model reactions support this mechanistic interpretation. Substituted, unsymmetrical phenols and bis-phenols react in a fashion that can be explained by engagement of the most readily available (non-hydrogen-bonded) hydroxyl in the phenol-ene process.

Original language	English (US)
Pages (from-to)	5596-5599
Number of pages	4
Journal	Organic Letters
Volume	18
Issue number	21
DOIs	https://doi.org/10.1021/acs.orglett.6b02830
State	Published - Nov 4 2016

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© 2016 American Chemical Society.

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abstract = "Benzynes produced thermally by the cycloisomerization of triyne-containing precursors [i.e., by the hexadehydro-Diels-Alder (HDDA) reaction] react with phenols at the carbon ortho to the hydroxyl in an enelike fashion. Following tautomerization of the intermediate cyclohexadienones, this produces biaryl derivatives. DFT calculations of model reactions support this mechanistic interpretation. Substituted, unsymmetrical phenols and bis-phenols react in a fashion that can be explained by engagement of the most readily available (non-hydrogen-bonded) hydroxyl in the phenol-ene process.",

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AU - Hoye, Thomas R.

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AB - Benzynes produced thermally by the cycloisomerization of triyne-containing precursors [i.e., by the hexadehydro-Diels-Alder (HDDA) reaction] react with phenols at the carbon ortho to the hydroxyl in an enelike fashion. Following tautomerization of the intermediate cyclohexadienones, this produces biaryl derivatives. DFT calculations of model reactions support this mechanistic interpretation. Substituted, unsymmetrical phenols and bis-phenols react in a fashion that can be explained by engagement of the most readily available (non-hydrogen-bonded) hydroxyl in the phenol-ene process.

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The Phenol-Ene Reaction: Biaryl Synthesis via Trapping Reactions between HDDA-Generated Benzynes and Phenolics

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