This proposal seeks to develop new oxidation reactions based on the metal promoted reactivity of a strong but kinetically inert oxidant, nitrous oxide. As such, nitrous oxide the potential to be a selective oxidant in fine chemical or pharmaceutical synthesis, but has the oxidizing power to act on numerous substrates. Nitrous oxide is readily available as a byproduct of nylon synthesis and has a low environmental impact; only nitrogen or nitrogen and water are generated upon oxidation. The substrates of choice for this work are transition metal-activated C-H bonds. This proposed work will attempt to utilize metal assisted nitrous oxide based oxidations to functionalize aliphatic, olefinic, and aromatic hydrocarbons. The preference for insertion of the oxygen atom of nitrous oxide into metal-hydride vs. metal-carbon bonds has not been thoroughly probed, nor the propensity for oxygen atom insertion over oxidation of the metal center. This work will investigate the above preferences, with a focus on known processes requiring oxidation of transition metal centers during turnover, and oxygen atom insertion into known metal-aryl- hydride and metal-alkyl-hydride compounds.
| Murphy, Jaclyn M; Lawrence, Joshua D; Kawamura, Kazumori et al. (2006) Ruthenium-catalyzed regiospecific borylation of methyl C-H bonds. J Am Chem Soc 128:13684-5 |
| Lawrence, Joshua D; Takahashi, Makoto; Bae, Chulsung et al. (2004) Regiospecific functionalization of methyl C-H bonds of alkyl groups in reagents with heteroatom functionality. J Am Chem Soc 126:15334-5 |
