Synthesis of 2-Substituted 1,2-Dihydronaphthalenes and 1,2-Dihydroanthracenes Using a Recyclable Molybdenum Dearomatization Agent

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• 作者：Jeffery T. Myers ; Philip J. Shivokevich ; Jared A. Pienkos ; Michal Sabat ; William H. Myers ; W. Dean Harman
• 刊名：Organometallics
• 出版年：2015
• 出版时间：July 27, 2015
• 年：2015
• 卷：34
• 期：14
• 页码：3648-3657
• 全文大小：481K
• ISSN：1520-6041

文摘

Polycyclic aromatic hydrocarbons (PAHs; e.g., naphthalene and anthracene) form stable 畏²-bound complexes with the dearomatizing fragment {TpMo(NO)(MeIm)} (where Tp = hydridotris(pyrazolyl)borate; MeIm = 1-methylimidazole). These complexes undergo protonation at the 伪 carbon followed by regioselective nucleophilic addition at the adjacent 尾 carbon. The nucleophile (a pyrrole or an enolate) adds stereoselectively, anti to the face of metal coordination. The resulting 1,2-dihydroarene ligand may be isolated via metal oxidation by iodine to provide the free 1,2-dihydroarene in moderate yield (鈭?0%), as well as TpMo(NO)(MeIm)(I), the precursor of the original PAH complex (鈭?0鈥?0%). Thus, a formal catalytic cycle for the dearomatization of naphthalene and anthracene has been demonstrated.