The use of different ligands allows the preparation of either allyl- or alkenylboronates by Pd-catalyzed borylation of allylic carbonates containing alkyne groups. Unprecedented borylative cyclisation to alkenylboronates takes place with PCy3. The difficult dissociation of NHC ligands allows borylation of carbonates in the presence of alkynes. Oxidation, regioselective Suzuki coupling, as well ...

[figure: see text] A conceptually new palladium-catalyzed amidation reaction is described for the synthesis of beta-amido ketones based on derailing the Wacker oxidation of enones. This reaction generates a new carbon-nitrogen bond via a palladium-catalyzed conjugate addition of a carbamate nucleophile to an enone. The regiocontrol, mild and neutral conditions, lack of preactivation of the nucl...

Methane oxidation is an important process to mitigate the emission of the greenhouse gas methane and further exacerbating of climate forcing. Both aerobic and anaerobic microorganisms have been reported to catalyze methane oxidation with only a few possible electron acceptors. Recently, new microorganisms were identified that could couple the oxidation of methane to nitrate or nitrite reduction...

Human cytochrome P450 (P450) 1B1 (CYP1B1) has recently been shown to be an important enzyme in the activation of diverse procarcinogens such as arylarenes, nitroarenes, and arylamines to reactive metabolites that cause DNA damage in the cells. However, it is not known whether this P450 enzyme also plays roles in the oxidation of certain drugs or model substrates commonly used in P450 assays. We...

Nicotine metabolism influences smoking behavior and differences in metabolism probably contribute to ethnic variability in lung cancer risk. We report here on the proportion of nicotine metabolism by cytochrome P450 2A6-catalyzed C-oxidation, UDP-glucuronosyl transferase 2B10 (UGT2B10)-catalyzed N-glucuronidation and flavin monooxygenase 3-catalyzed N-oxidation in five ethnic/racial groups and ...

A number of hydrazine derivatives were tested as substrates for the purified liver microsomal FAD-containing monooxygenase and the kinetic properties of the oxidation reactions were partially characterized. Only 1,l-dimethylhydrazine, l-methyl-l-phenylhydrazine, and the N-aminoheterocyclic hydrazines are oxidized as effectively as N,N-dimethylaniline, one of the best N-methylamine substrates fo...

The fundamental reaction mechanism of cytochrome P450 2A6 (CYP2A6)-catalyzed N-methylhydroxylation of (S)-(-)-nicotine and the free energy profile have been studied by performing pseudobond first-principles quantum mechanical/molecular mechanical (QM/MM) reaction-coordinate calculations. In the CYP2A6-(S)-(-)-nicotine binding structures that allow for 5'-hydroxylation, the N-methyl group is als...

We report the studies on the mechanism of oxidation of 3',4'-dihydroxy-l-phenylalanine (l-DOPA) to neurotoxic dopachrome catalyzed by enzyme horseradish peroxidase (EC 1.11.1.7) using the kinetic (KIE), and solvent (SIE), isotope effect methods. For kinetic studies two specifically deuterated isotopomers: [2',5',6'-2H3]-l-DOPA was synthesized by the acid catalyzed isotopic exchange between nati...

Recent work in our laboratory showed that products formed by the antibody-catalyzed water-oxidation pathway can kill bacteria. Dihydrogen peroxide, the end product of this pathway, was found to be necessary, but not sufficient, for the observed efficiency of bacterial killing. The search for further bactericidal agents that might be formed along the pathway led to the recognition of an oxidant ...

The first mercury-catalyzed synthesis of 1,2-diketones by alkyne oxidation has been developed. This inexpensive method extends the potential mercury catalysis and allows rapid construction various α-carbonyl amides in good yields with high functional group tolerance.