Oxidation of annelated diarylamines: Analysis of reaction pathways to nitroxide diradical and spirocyclic products

Andrzej Rajca, Kouichi Shiraishi, Przemysław J. Boratyński, Maren Pink, Makoto Miyasaka, Suchada Rajca

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Oxidation of diaryldiamine 2, a tetrahydrodiazapentacene derivative, provides diarylnitroxide diradical 1 accompanied by an intermediate nitroxide monoradical and a multitude of isolable diamagnetic products. DFT-computed tensors for EPR spectra and paramagnetic 1H NMR isotropic shifts for nitroxide diradical 1 show good agreement with the experimental EPR spectra in rigid matrices and paramagnetic 1H NMR spectra in solution, respectively. Examination of the diamagnetic products elucidates their formation via distinct pathways involving C-O bond-forming reactions, including Baeyer-Villiger-type oxidations. An unusual diiminoketone structure and two spirocyclic structures of the predominant diamagnetic products are confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as 1H, 13C, and 15N NMR chemical shifts and electronic absorption spectra.

Original languageEnglish (US)
Pages (from-to)8447-8457
Number of pages11
JournalJournal of Organic Chemistry
Volume76
Issue number20
DOIs
StatePublished - Oct 21 2011

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Nuclear magnetic resonance
Discrete Fourier transforms
Oxidation
Paramagnetic resonance
X ray crystallography
Chemical shift
Tensors
Absorption spectra
Derivatives

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Oxidation of annelated diarylamines : Analysis of reaction pathways to nitroxide diradical and spirocyclic products. / Rajca, Andrzej; Shiraishi, Kouichi; Boratyński, Przemysław J.; Pink, Maren; Miyasaka, Makoto; Rajca, Suchada.

In: Journal of Organic Chemistry, Vol. 76, No. 20, 21.10.2011, p. 8447-8457.

Research output: Contribution to journalArticle

Rajca, Andrzej ; Shiraishi, Kouichi ; Boratyński, Przemysław J. ; Pink, Maren ; Miyasaka, Makoto ; Rajca, Suchada. / Oxidation of annelated diarylamines : Analysis of reaction pathways to nitroxide diradical and spirocyclic products. In: Journal of Organic Chemistry. 2011 ; Vol. 76, No. 20. pp. 8447-8457.
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