4-(Dimethylamino)pyridine (DMAP) as an Acid-Modulated Donor Ligand for PAH Dearomatization

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• 作者：Jeffery T. Myers ; Steven J. Dakermanji ; Timothy R. Chastanet ; Philip J. Shivokevich ; Laura J. Strausberg ; Michal Sabat ; William H. Myers ; W. Dean Harman
• 刊名：Organometallics
• 出版年：2017
• 出版时间：February 13, 2017
• 年：2017
• 卷：36
• 期：3
• 页码：543-555
• 全文大小：540K
• ISSN：1520-6041

文摘

The dearomatization of naphthalene and anthracene is explored by their η² coordination to {TpMo(NO)(MeIm)} and {TpMo(NO)(DMAP)} (where Tp = hydridotris(pyrazolyl)borate, MeIm = 1-methylimidazole, and DMAP = 4-(dimethylamino)pyridine). The DMAP and MeIm complexes have nearly identical redox properties and abilities to bind these polycyclic aromatic hydrocarbons (PAHs), but unlike MeIm, the DMAP ligand can be protonated at N while remaining bound to the metal. This action enhances the π-acidic properties of DMAP, resulting in greater stability of the molybdenum toward oxidation by acid. Utilizing this feature of the DMAP ligand, several new 1,2-dihydronaphthalenes and 1,2-dihydroanthracenes were prepared. Furthermore, it was found that acetals and Michael acceptors could function as electrophiles for the PAHs using the DMAP system, resulting in several new mono- and 1,4-dialkylated products.