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.

Comments

©2014 American Chemical Society

Additional Comments

NSF grant #s: CHE07-42801, CHE11-48992, CHE97-09183; American Chemical Society Petroleum Research Fund grant #: 48388-AC4

ORCID ID

0000-0002-0566-0820

ResearcherID

V-6501-2018

DOI

10.1021/ja507517g

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