4-(Dimethylamino)pyridine (DMAP) as an Acid-Modulated Donor Ligand for PAH DearomatizationClick to copy article linkArticle link copied!
- Jeffery T. Myers
- Steven J. Dakermanji
- Timothy R. Chastanet
- Philip J. Shivokevich
- Laura J. Strausberg
- Michal Sabat
- William H. Myers
- W. Dean Harman
Abstract
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.
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