Triarylmethanols bearing bulky aryl groups and the NOESY/EXSY experimental observation of two-ring-flip mechanism for helicity reversal of molecular propellers

Victor M Tormyshev; Alexander M Genaev; Georgy E Sal'nikov; Olga Yu Rogozhnikova; Tatiana I Troitskaya; Dmitry V Trukhin; Victor I Mamatyuk; Dmitry S Fadeev; Howard J Halpern

doi:10.1002/ejoc.201101243

Triarylmethanols bearing bulky aryl groups and the NOESY/EXSY experimental observation of two-ring-flip mechanism for helicity reversal of molecular propellers

European J Org Chem. 2012 Jan;2012(3):10.1002/ejoc.201101243. doi: 10.1002/ejoc.201101243.

Authors

Victor M Tormyshev¹, Alexander M Genaev, Georgy E Sal'nikov, Olga Yu Rogozhnikova, Tatiana I Troitskaya, Dmitry V Trukhin, Victor I Mamatyuk, Dmitry S Fadeev, Howard J Halpern

Affiliation

¹ 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

Triarylmethanols - the direct precursors of persistent trityl radicals - are racemic mixtures of chiral three-bladed molecular propellers. Depending on bulkiness of aryl groups they exhibit various liabilities to interconversion, the half- life time of room temperature racemization varying in a range between 8.4 hours and 1.32 years. NOESY/EXSY experiment performed on two representative models strongly supports the two-ring flip mechanism for the configurational interchange.

Keywords: 2D NOESY/EXSY; activation parameters; chirality; epimerization mechanism; triarylmethanols.

Abstract

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