Transition-Metal-Free C–H Hydroxylation of Carbonyl Compounds

Transition metal and reductant free α-C­(sp3)–H hydroxylation of carbonyl compounds are reported. This method is promoted by commercially available inexpensive KO-<i>t</i>-Bu and atmospheric air as an oxidant at room temperature. This unified strategy is also very facile for hydroxylation of various carbonyl compound derivatives to obtain quaternary hydroxyl compounds in excellent yield. A preliminary mechanistic investigation, supported by isotope labeling and computational studies, suggests the formation of a peroxide bond and its cleavage by in situ generated enolate

Transition-Metal-Free C–H Hydroxylation of Carbonyl Compounds

Transition metal and reductant free α-C­(sp3)–H hydroxylation of carbonyl compounds are reported. This method is promoted by commercially available inexpensive KO-<i>t</i>-Bu and atmospheric air as an oxidant at room temperature. This unified strategy is also very facile for hydroxylation of various carbonyl compound derivatives to obtain quaternary hydroxyl compounds in excellent yield. A preliminary mechanistic investigation, supported by isotope labeling and computational studies, suggests the formation of a peroxide bond and its cleavage by in situ generated enolate

Unravelling the role of microorganisms in arsenic mobilization using metagenomic techniques

The contamination of groundwaters, abstracted for drinking and irrigation, by sediment-derived arsenic, threatens the health of tens of millions worldwide. Microbial processes are accepted as playing a key role in arsenic mobilisation from sediments into groundwaters, but the precise biogeochemical mechanisms remain a subject of debate. A combination of field investigations, coupled to laboratory experimentation with sediment samples using “microcosm” approaches, has provided a significant body of evidence supporting a key role for anaerobic metal-reducing bacteria in the reductive mobilization of arsenic in aquifers in West Bengal, Cambodia, Vietnam and Bangladesh. The application of high-throughput next generation sequencing, combined with metagenomic reconstructions and other “omics” techniques from the life sciences is shedding new insight into the processes at play, and identifying new mircoorganisms and coupled biogeochemical processes that control the solubility of arsenic in Asian aquifers

Iron-Catalyzed Batch/Continuous Flow C–H Functionalization Module for the Synthesis of Anticancer Peroxides

Iron-catalyzed dehydrogenative cross-coupling of carbonyl compounds with aliphatic peroxide was developed under mild conditions. A library of linear alkylated and arylated peroxides are synthesized in good to excellent yield. This method is highly selective and general for a range of biologically important derivatives of 2-oxindole, barbituric acid, and 4-hydroxy coumarin with a good functional group tolerance and without the cleavage of the peroxide bond. This peroxidation reaction is upscalable to grams and also synthesizable in continuous flow with increased safety in short duration. Mechanistic investigation reveals Fe-(II) undergoes redox type process to generate the radical intermediates, which subsequently recombine selectively to form the stable peroxides. The potential of peroxides is evaluated by cell viability assay and found to exhibit the good anticancer activity with minimum IC₅₀= 5.3 μM

Iron-Catalyzed Batch/Continuous Flow C–H Functionalization Module for the Synthesis of Anticancer Peroxides

Iron-catalyzed dehydrogenative cross-coupling of carbonyl compounds with aliphatic peroxide was developed under mild conditions. A library of linear alkylated and arylated peroxides are synthesized in good to excellent yield. This method is highly selective and general for a range of biologically important derivatives of 2-oxindole, barbituric acid, and 4-hydroxy coumarin with a good functional group tolerance and without the cleavage of the peroxide bond. This peroxidation reaction is upscalable to grams and also synthesizable in continuous flow with increased safety in short duration. Mechanistic investigation reveals Fe-(II) undergoes redox type process to generate the radical intermediates, which subsequently recombine selectively to form the stable peroxides. The potential of peroxides is evaluated by cell viability assay and found to exhibit the good anticancer activity with minimum IC₅₀= 5.3 μM