Generation of Trityl Radicals by Nucleophilic Quenching of Tris(2,3,5,6-tetrathiaaryl)methyl Cations and Practical and Convenient Large-Scale Synthesis of Persistent Tris(4-carboxy-2,3,5,6-tetrathiaaryl)methyl Radical

Olga Yu Rogozhnikova; Vladimir G Vasiliev; Tatiana I Troitskaya; Dmitry V Trukhin; Tatiana V Mikhalina; Howard J Halpern; Victor M Tormyshev

doi:10.1002/ejoc.201300176

Generation of Trityl Radicals by Nucleophilic Quenching of Tris(2,3,5,6-tetrathiaaryl)methyl Cations and Practical and Convenient Large-Scale Synthesis of Persistent Tris(4-carboxy-2,3,5,6-tetrathiaaryl)methyl Radical

European J Org Chem. 2013 Jun 1;2013(16):3347-3355. doi: 10.1002/ejoc.201300176.

Authors

Olga Yu Rogozhnikova¹, Vladimir G Vasiliev¹, Tatiana I Troitskaya¹, Dmitry V Trukhin¹, Tatiana V Mikhalina¹, Howard J Halpern², Victor M Tormyshev³

Affiliations

¹ Vorozhtsov Novosibirsk Institute of Organic Chemistry, 9 Acad. M.A. Lavrentjev Ave., Novosibirsk 630090, Russia.
² The Center for EPR Imaging in vivo Physiology, Department of Radiation and Cellular Oncology, the University of Chicago, Chicago, IL 60637, USA.
³ Vorozhtsov Novosibirsk Institute of Organic Chemistry, 9 Acad. M.A. Lavrentjev Ave., Novosibirsk 630090, Russia ; Department of Natural Sciences, Novosibirsk State University, 2 Pirogov St., Novosibirsk 630090, Russia.

Abstract

Tris(2,3,5,6-tetrathiaaryl)methyl cations, which were generated from the corresponding triarylmethanols in the presence of strong acids, underwent reaction with nucleophiles to give trityl radicals, as the product of a one-electron reduction of the carbocation. Depending on the nature of the nucleophile, the only byproducts were either diamagnetic quinone methides or asymmetrical monosubstituted trityl radicals. Herein, we report a protocol for the large-scale synthesis of the Finland trityl, which has the advantage of high overall yield and reproducibility.

Keywords: Carbocations; Quinones; Radicals; Reaction mechanisms; Synthesis design.

Abstract

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