Selectivity and Isotope Effects in Hydronation of a Naked Aryl Anion

Autor:	Charles L. Perrin, Gabriel J. Reyes-Rodríguez
Rok vydání:	2014
Předmět:	chemistry.chemical_classification Diradical Aryl Iodide Protonation General Chemistry Photochemistry Biochemistry Medicinal chemistry Catalysis chemistry.chemical_compound Colloid and Surface Chemistry chemistry Enediyne Reactivity (chemistry) Acetonitrile Selectivity
Zdroj:	Journal of the American Chemical Society. 136:15263-15269
ISSN:	1520-5126 0002-7863
DOI:	10.1021/ja507517g
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::e0368681e7cb993d75c2db918fb5951e https://doi.org/10.1021/ja507517g Zobrazit plný text záznamu