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C-C cross-coupling reactions of trityl radicals: Spin density delocalization, exchange coupling, and a spin label.

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Meyer,  A.
Research Group of Electron Paramagnetic Resonance, MPI for Biophysical Chemistry, Max Planck Society;

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Citation

Fleck, N., Hett, T., Brode, J., Meyer, A., Richert, S., & Schiemann, O. (2019). C-C cross-coupling reactions of trityl radicals: Spin density delocalization, exchange coupling, and a spin label. The Journal of Organic Chemistry, 84(6), 3293-3303. doi:10.1021/acs.joc.8b03229.


Cite as: http://hdl.handle.net/21.11116/0000-0003-4B1E-9
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 magnets or quantum computing devices.