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Metal-mediated [2+3] cycloaddition of nitrones to palladium-bound isonitrilesстатья
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: 20 апреля 2022 г.
- Авторы: Luzyanin K.V., Tskhovrebov A.G., Guedes da Silva M.F.C, Haukka M., Pombeiro A.J.L, Kukushkin V.Y.
- Журнал: Chemistry - A European Journal
- Том: 15
- Номер: 24
- Год издания: 2009
- Издательство: John Wiley & Sons Ltd.
- Местоположение издательства: United Kingdom
- Первая страница: 5969
- Последняя страница: 5978
- DOI: 10.1002/chem.200802623
- Аннотация: The reactions between equimolar amounts of cis-[PdCl 2(C≡NR)2] (R=cyclohexyl (Cy) 1, tBu 2, 2,6-Me 2C6H3 (Xyl) 3) and the acyclic nitrones O +N(R2)=C(H)R3 (R2=Me 5, R 2=CH2Ph 6, R3=4-MeC6H4) proceeded in C6H6 at 5 °C for around 4 h and then the reaction systems were maintained at 20-25 °C for 20 h to provide the carbene complexes [PdCl2C(ONR2CcHR 3)=NdR(C≡ NR)(CcéNd)] (8-13) in good yields (54-70%). The latter species originated from the previously unreported metalmediated [2+3] cycloaddition of nitrones to coordinated isonitriles. For the reactions of cis-[PdCl2(C ≡NR)2] (1-3) and 5 or 6 performed in C6H6 at 20-25 °C, the selectivity of the cycloaddition was lost, and the reactions gave mixtures of 8-13 and the complexes [PdCl2N(R2)=CHR 3(C≡NR)] (14-19, ca. 75%) derived from intramolecular deoxygenation of the nitrones. The reactions of equimolar amounts of cis-[PdCl2(C≡NR)2] (1-3 and R=4-MeOC 6H4 4) and the nonaromatic cyclic nitrone -O+Na= CHCH2CH2C bMe2Na-Cb) (7) in CHCl3 at 5 °C for around 2 h led to the carbene species [PdCl 2C(ONaCMe2CH2CH2C bH)= NeR(C≡NR)(Nae-Cb)(C be-Ne)] (21-24), isolated in yields of 78-92%. When the reactions of cis-[PdCl2(C≡NR)2] (1-4) and 7 (1:1 molar ratio) were performed in CHCl3 at 20-25 °C for around 1 h, the carbenes 21-24 and the complexes [PdCl2NfCMe 2CH2CH2CgH(C≡NR)-(N f-Cg)] (25-28, ca. 35%), derived from the deoxygenation of 7, were identified by ESI+-MS and 1H NMR analysis (after redissolution in CDCl3). The reactions of cis-[PdCl 2(C≡;NR)2] (1-4) and 7 (1:2 molar ratio) in CHCl3 at 5 °C furnished mixtures of [PdCl2C(ON aCMe2CH2CH2CbH)= N eR(NfCMe2CH2CH2C gH)(Na-Cb)-Cb-Ne)(N f-Cg)] (29-32; ca. 25-30%), 25-28 (ca. 10-15%), and [PdCl2(ONaCMe2CH2CH 2CbH)2(Na-Cb)]. The same reactions at room temperature afforded the complex [PdCl2(N fCMe2CH2CH2CgH) 2(Nf-Cg)] (33; ca. 20%) in a mixture with 29-32 (ca. 5-10%) and 25-28. © 2009 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.
- Добавил в систему: Цховребов Александр Георгиевич