Chemistry and Physics Faculty Articles
Title
Selectivity and Isotope Effects in Hydronation of a Naked Aryl Anion
Document Type
Article
Publication Date
10-29-2014
Publication Title
Journal of the American Chemical Society
ISSN
0002-7863
Volume
136
Issue/No.
43
First Page
15263
Last Page
15269
Abstract
An aryl anion is produced by rapid addition of iodide to the p-benzyne diradical formed by cycloaromatization of an enediyne. The aryl anion is then hydronated (protonated or deuteronated) to form 1-iodotetrahydronaphthalene. Hydrons can be incorporated not only from water but also from such weak acids as dimethyl sulfoxide and acetonitrile. The relative reactivity of each pair of hydron donors is evaluated from competition experiments. A low selectivity is observed and taken as evidence for a high basicity of the aryl anion. Moreover, the same relative reactivities are obtained with Bu4NI as with LiI; therefore the species that undergoes hydronation is not an aryllithium but a naked aryl anion. These studies thus characterize the reactivity of a naked aryl anion in solution and contrast it with the reactivity of an aryllithium or an aryl Grignard.
Additional Comments
NSF grant #s: CHE07-42801, CHE11-48992, CHE97-09183; American Chemical Society Petroleum Research Fund grant #: 48388-AC4
NSUWorks Citation
Perrin, C. L., & Reyes-Rodriguez, G. J. (2014). Selectivity and Isotope Effects in Hydronation of a Naked Aryl Anion. Journal of the American Chemical Society, 136, (43), 15263 - 15269. https://doi.org/10.1021/ja507517g. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/259
ORCID ID
0000-0002-0566-0820
ResearcherID
V-6501-2018
DOI
10.1021/ja507517g
Comments
©2014 American Chemical Society