Synthesis of Heterocyclic Ligands by Diheterocyclization at the Rhenium(I) Allenylidene [(triphos)(CO)2Re{C=C=CPh2}](OSO2CF3). 1. Reactivity with Dipolar N<

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• 作者：Nicoletta Mantovani ; Paola Bergamini ; Andrea Marchi ; Lorenza Marvelli ; Roberto Rossi ; Valerio Bertolasi ; Valeria Ferretti ; Isaac de los Rios ; and Maurizio Peruzzini
• 刊名：Organometallics
• 出版年：2006
• 出版时间：January 16, 2006
• 年：2006
• 卷：25
• 期：2
• 页码：416 - 426
• 全文大小：262K
• 年卷期：v.25,no.2(January 16, 2006)
• ISSN：1520-6041

文摘

1,2,3-Diheterocyclizations at the allenylidene ligand in the complex [(triphos)(CO)₂Re{C=C=CPh₂}]OTf (1; triphos = MeC(CH₂PPh₂)₃, OTf = OSO₂CF₃) readily occur upon reacting 1 with N,N-heterocyclessuch as 1H-benzotriazole, 2-aminopyridine, and 2-aminothiazole. The reaction of 1 with 1H-benzotriazoleleads to [(triphos)(CO)₂Re{C=C(H)C(Ph)}]N(C₆H₄)N=N}]OTf (4). Deprotonation of 4 with sodiummethoxide in tetrahydrofuran at room temperature yields the alkynyl derivative [(triphos)(CO)₂Re{CCC(Ph)₂(NC₆H₄N=N)}] (5) via ring opening of the triazaindenyl moiety in 4. Reaction of 1 with2-aminopyridine or 2-aminothiazole in CH₂Cl₂ leads to the heterobicyclic compounds [(triphos)(CO)₂Re{C=C(H)C(Ph)₂N(H)C(CH)₄N}]OTf (6) and [(triphos)(CO)₂Re{C=C(H)C(Ph)₂N(H)CS(CH)₂N}]OTf(8), respectively. Both complexes undergo regioselective deprotonation at the N-H heterocycle groupby treatment with sodium methoxide in THF, giving the neutral species [(triphos)(CO)₂Re{C=C(H)C(Ph)₂NC(CH)₄N}] (7) and [(triphos)(CO)₂Re{C=C(H)C(Ph)₂NCS(CH)₂N}] (9), respectively. The X-raystructures of the new organorhenium species 4 and 7-9 have been determined, which have confirmedthat the addition of the NH bond of the N,N-heterocycle occurs always across the C-C double bondof the allenylidene chain.