C-C Cross-Coupling Reactions of Trityl Radicals: Spin Density Delocalization, Exchange Coupling, and a Spin Label

The Journal of Organic Chemistry
Nico FleckOlav Schiemann

Abstract

Organic radicals are usually highly reactive and short-lived species. In contrast, tetrathiatriarylmethyl radicals, the so-called trityl- or TAM-radicals, are stable and do survive over longer times even under in-cell conditions. In addition, they show strong EPR signals, have long phase memory times at room temperature, and are reporters on local oxygen and proton concentrations. These properties facilitated their use for magnetic resonance imaging, dynamic nuclear polarization, and spin-labeling EPR under in-cell conditions. Thus, synthetic approaches are required for functionalization of TAM radicals tailored to the desired application. However, most TAM derivatives reported in the literature are based on esterification of the Finland trityl, which is prone to hydrolysis. Here, we report on an approach in which TAM is site-selective iodinated and subsequently C-C cross-coupled to various building blocks in a modular approach. This yields conjugated trityl compounds such as a trityl attached to a porphyrin, an alkinyl functionalized trityl radical, and a strongly exchange-coupled trityl biradical. This synthesis approach thus has implications not only for magnetic resonance spectroscopy but also for the design of molecular ma...Continue Reading

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Citations

Jul 31, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·J Jacques JassoyOlav Schiemann
Aug 19, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Kevin KoppNico Fleck
Jul 19, 2020·Chemistry : a European Journal·Oliver NoldenSabine Richert
May 28, 2021·The Journal of Organic Chemistry·Li ChenYangping Liu
Oct 28, 2020·The Journal of Organic Chemistry·Thanh Binh NguyenPascal Retailleau
Jul 24, 2020·The Journal of Organic Chemistry·Urikhan SanzhaevaBenoit Driesschaert
Jan 14, 2022·Physical Chemistry Chemical Physics : PCCP·Maria Grazia ConcilioLucio Frydman

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