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Nitration of Heteroaryltrimethyltins by Tetranitromethane and Dinitrogen Tetroxide: Mechanistic Aspects, Scope and Limitations
Author(s) -
Fargeas Valérie,
Favresse Fabien,
Mathieu Didier,
Beaudet Isabelle,
Charrue Pierre,
Lebret Bruno,
Piteau Marc,
Quintard JeanPaul
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200210611
Subject(s) - tetranitromethane , chemistry , nitration , furan , pyrimidine , photochemistry , thiophene , computational chemistry , medicinal chemistry , organic chemistry , stereochemistry
The nitration of 2‐(trimethylstannyl)heteroarenes by tetranitromethane (TNM) or dinitrogen tetroxide has been shown to be possible when the HOMO energy of the heteroaryltin is high enough to allow the formation of the corresponding radical cation. The reaction proceeds through a charge‐transfer complex between heteroaryltin and TNM, followed by a single‐electron transfer, which is enhanced under sunlamp irradiation. Accordingly, 2‐nitrobenzo[ b ]furan, 2‐nitrobenzo[ b ]thiophene, 2‐nitropyridine and 2‐nitroindoles were obtained by this method. However, the nitration of 2‐stannylated pyrimidine or of stannylated 1,3,5‐triazines has been shown to be impossible, due to the low energy of their HOMO orbitals. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)