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

Sean P. Ross; Beeraiah Baire; Thomas R. Hoye

doi:10.1021/acs.orglett.7b02888

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

Sean P. Ross, Beeraiah Baire, Thomas R. Hoye

Chemistry (Twin Cities)

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

12 Scopus citations

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 β-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.

Original language	English (US)
Pages (from-to)	5705-5708
Number of pages	4
Journal	Organic Letters
Volume	19
Issue number	20
DOIs	https://doi.org/10.1021/acs.orglett.7b02888
State	Published - Oct 20 2017

Bibliographical note

Funding Information:
This work was supported by the U.S. Department of Health and Human Services, National Institute of General Medical Sciences (GM-65597). NMR spectral data were obtained with an instrument procured with a grant from the National Institutes of Health Shared Instrumentation Grant program (S10OD011952).

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© 2017 American Chemical Society.

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10.1021/acs.orglett.7b02888

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5650509

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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 β-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.",

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N2 - 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. Finally, amino alcohols react at either of their N- or O atoms, depending upon the extent of internal hydrogen bonding.

AB - 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. Finally, amino alcohols react at either of their N- or O atoms, depending upon the extent of internal hydrogen bonding.

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

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