Nitrene–nitrene rearrangement under thermal, photochemical, and electron-impact conditions: the 2-azidopyridines/tetrazolo[1,5-a]pyridines

Wentrup, Curt, Braybrook, Carl, Liu, Shanshan, Tzschucke, C. Christoph, Dargelos, Alain and Bégué, Didier (2016) Nitrene–nitrene rearrangement under thermal, photochemical, and electron-impact conditions: the 2-azidopyridines/tetrazolo[1,5-a]pyridines. European Journal of Organic Chemistry, . doi:10.1002/ejoc.201600655


Author Wentrup, Curt
Braybrook, Carl
Liu, Shanshan
Tzschucke, C. Christoph
Dargelos, Alain
Bégué, Didier
Title Nitrene–nitrene rearrangement under thermal, photochemical, and electron-impact conditions: the 2-azidopyridines/tetrazolo[1,5-a]pyridines
Formatted title
Nitrene–nitrene rearrangement under thermal, photochemical, and electron-impact conditions: the 2-azidopyridines/tetrazolo[1,5-a]pyridines
Journal name European Journal of Organic Chemistry   Check publisher's open access policy
ISSN 1099-0690
1434-193X
Publication date 2016-07-28
Year available 2016
Sub-type Article (original research)
DOI 10.1002/ejoc.201600655
Open Access Status Not Open Access
Total pages 8
Place of publication Weinheim, Germany
Publisher Wiley - V C H Verlag GmbH & Co. KGaA
Collection year 2017
Language eng
Formatted abstract
15N-Labeling demonstrates that the two nitrogen atoms in the 2-pyridylnitrene radical cation 2·+ become equivalent prior to fragmentation in the mass spectrometer. Furthermore, the mass spectra of 6- and 7-tetrazolo[1,4-a]pyridine are identical, as are those of 5- and 8-tetrazolo[1,5-a]pyridine, thereby again demonstrating interconversion of the nitrogen atoms in 2-pyridylnitrenes. These rearrangements parallel the reactions established under thermal (flash vacuum pyrolysis) and photochemical condition. Calculations of the energies of ground and transition states at the CASPT2(7,8) level support the notion that 2-pyridylnitrenes undergo very easy and exothermic ring expansion to 1,3-diazacycloheptatetraene 3, both in the neutrals and the radical cations. In addition, the ring opening to 4-cyanobutadienylnitrene 4 can take place in both the neutrals and the radical cations with modest activation barriers.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
School of Chemistry and Molecular Biosciences
 
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Created: Fri, 29 Jul 2016, 10:24:30 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences