4-(Dimethylamino)pyridine (DMAP) as an Acid-Modulated Donor Ligand for PAH Dearomatization
| Autor: | W. Dean Harman, Laura Strausberg, Jeffery T. Myers, Philip J. Shivokevich, Michal Sabat, Steven J. Dakermanji, William H. Myers, Timothy R. Chastanet |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
Anthracene
010405 organic chemistry Ligand Organic Chemistry Protonation 010402 general chemistry 01 natural sciences Redox Medicinal chemistry 0104 chemical sciences Inorganic Chemistry Metal chemistry.chemical_compound chemistry visual_art Pyridine Electrophile visual_art.visual_art_medium Organic chemistry Physical and Theoretical Chemistry Naphthalene |
| Zdroj: | Organometallics. 36:543-555 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/acs.organomet.6b00780 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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