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PtII-mediated nitrile-tetramethylguanidine coupling as a key step for a novel synthesis of 1,6-dihydro-1,3,5-triazinesстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Gushchin P.V., Bokach N.A., Luzyanin K.V., Nazarov A.A., Haukka M., Kukushkin V.Yu
- Журнал: Inorganic Chemistry
- Том: 46
- Номер: 5
- Год издания: 2007
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 1684
- Последняя страница: 1693
- DOI: 10.1021/ic061884b
- Аннотация: The coupling between tetramethylguanidine, HN=C(NMe2) 2, and coordinated organonitriles in the platinum(II) complexes cis/trans-[PtCl2(RCN)2] (R = Me, Et, Ph) proceeds rapidly under mild conditions to afford the diimino compounds containing two N-bound monodentate 1,3-diaza-1,3-diene ligands [PtCl2NH=C(R)N=C(NMe 2)22] (R = Et, frans-1; R = Ph, trans-2; R = Me, cis-3; R = Et, cis-4), and this reaction is the first observation of metal-mediated nucleophilic addition of a guanidine to ligated nitrile. Complexes 1-4 were characterized by elemental analyses (C, H, N), X-ray diffraction, FAB mass spectrometry, IR, and 1H and 13C1H NMR spectroscopies; assignment of signals from E/Z-forms of 1,3-diaza-1,3-diene ligands and verification of routes for their Z ⇆ E isomerization in solution were performed using 2D 1H, 1H-COSY, 1H,13C-HETCOR, and 1D NOE NMR experiments. The newly formed and previously unknown 1,3-diaza-1,3-dienes NH=C(R)N=C(NMe2)2 were liberated from the platinum(II) complexes [PtCl2NH=C(R)N=C(NMe2)2 2] (1-3) by substitution with 2 equiv of 1,2-bis-(diphenylphosphino) ethane (dppe) to give the uncomplexed HN=C(R)N=C(NMe2)2 species (5-7) in solution and the solid [Pt-(dppe)2](Cl)2. The former were utilized in situ, after filtration of the latter, in the reaction with 1,3-di-p-tolylcarbodiimide, (p-tol)N=C=N(tol-p), in CDCl 3 to generate (6E)-N,N-dimethyl-1-(4-methylphenyl)-6-[(4- methylphenyl)imino]-1,6-dihydro-1,3,5-triazin-2-amines) (8-10) due to the [4 + 2]-cycloaddition accompanying elimination of HNMe2. The formulation of 8-10 is based on ESI-MS, 1H, 13C1H NMR, and X-ray crystal structures determined for 9 and 10. The reaction of 1,3-diaza-1,3-dienes with 1,3-di-p-tolylcarbodiimide, described in this article, constitutes a novel synthetic approach to a useful class of heterocyclic species like 1,6-dihydro-1,3,5-triazines. © 2007 American Chemical Society.
- Добавил в систему: Назаров Алексей Анатольевич