Flash vacuum thermolysis of N-(3- and 4-pyridylmethylidene)-tert-butylamines: mechanisms of formation of pyrrolopyridines and naphthyridines

Justyna, Katarzyna, Leśniak, Stanisław, Nazarski, Ryszard B., Rachwalski, Michał, Vu, Thien Y., Huynh, Thi Kieu Xuan, Khayar, Saïd, Dargelos, Alain, Chrostowska, Anna and Wentrup, Curt (2014) Flash vacuum thermolysis of N-(3- and 4-pyridylmethylidene)-tert-butylamines: mechanisms of formation of pyrrolopyridines and naphthyridines. European Journal of Organic Chemistry, 2014 14: 3020-3027. doi:10.1002/ejoc.201400112


Author Justyna, Katarzyna
Leśniak, Stanisław
Nazarski, Ryszard B.
Rachwalski, Michał
Vu, Thien Y.
Huynh, Thi Kieu Xuan
Khayar, Saïd
Dargelos, Alain
Chrostowska, Anna
Wentrup, Curt
Title Flash vacuum thermolysis of N-(3- and 4-pyridylmethylidene)-tert-butylamines: mechanisms of formation of pyrrolopyridines and naphthyridines
Formatted title
Flash vacuum thermolysis of N-(3- and 4-pyridylmethylidene)-tert-butylamines: mechanisms of formation of pyrrolopyridines and naphthyridines
Journal name European Journal of Organic Chemistry   Check publisher's open access policy
ISSN 1434-193X
1099-0690
Publication date 2014-05-01
Sub-type Article (original research)
DOI 10.1002/ejoc.201400112
Volume 2014
Issue 14
Start page 3020
End page 3027
Total pages 8
Place of publication Weinheim, Germany
Publisher Wiley - V C H Verlag
Language eng
Formatted abstract
Pyrrolopyridines and naphthyridines are formed by flash vacuum thermolysis (FVT) of 3- and 4-pyridylmethylidene-tert-butylimines 8 and 15. Elimination of a methyl radical generates resonance stablized 2-azaallyl radicals a1 and b1. The formation of pyrrolopyridines 9, 16 and 17 is rationalized in terms of cyclization of 1-aziridinyl radicals a2 and b2. Formation of naphthyridine 10 from imine 8, and of 11 and 18 from imine 15, are in accord with cyclization of 1-azaallyl radicals a6 and b9. Formation of naphthyridine 11 from 8, and of 10 and 19 from 15, indicate the operation of the spiro-cyclization pathways forming intermediates a9 and b14. Formation of the 1,8-naphthyridine 20 (3 %) indicates a rearrangement through aziridine b22 and biradical b23. DFT calculations at the CAM-B3LYP/6-311G(d,p) level support the proposed reaction mechanisms.
Keyword High-temperature reactions
Radicals
Rearrangement
Heterocycles
Photoelectron spectroscopy
Density functional calculations
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Fri, 21 Mar 2014, 20:29:30 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences