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

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 pr...

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Bibliographic Details
Published in:Organometallics 2017-02, Vol.36 (3), p.543-555
Main Authors: Myers, Jeffery T, Dakermanji, Steven J, Chastanet, Timothy R, Shivokevich, Philip J, Strausberg, Laura J, Sabat, Michal, Myers, William H, Harman, W. Dean
Format: Article
Language:English
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Summary: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.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.6b00780