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.
Bibliographical noteFunding 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).