Sulfur-Directed α-C(sp3)-H Amidation of Pyrrolidines with Dioxazolones under Rhodium Catalysis.

Site-selective functionalization of saturated N-heterocycles such as pyrrolidines is a central topic in organic synthesis and drug discovery. We herein report the sulfur-assisted rhodium(III)-catalyzed sp3 C-H amidation of pyrrolidines with dioxazolones as amidating agents. The amenability of the thioamide directing group is elucidated by a series of control experiments.

Catalyst-Controlled C-H Allylation and Annulation of 2-Aryl Quinazolinones with 2-Methylidene Cyclic Carbonate.

The site-selective modification of quinazolinone as a privileged bicyclic N-heterocycle is an attractive topic in medicinal chemistry and material science. We herein report the ruthenium(II)-catalyzed C-H allylation of 2-aryl quinazolinones with 2-methylidene cyclic carbonate. In addition, tandem C-H allylation and annulation are achieved under rhodium(III) catalysis, resulting in the formation of tetracyclic quinazolinones including a tertiary carbon center. Post-transformations of the synthesized products demonstrate the potential of the developed methodology. A series of mechanistic investigations were also performed.

Synthesis of 2-Formyl Carbazoles via Tandem Reaction of Indolyl Nitrones with 2-Methylidene Cyclic Carbonate.

The synthesis of functionalized carbazoles as privileged nitrogen heterocycles has emerged as a central topic in drug discovery and material science. We herein disclose the rhodium(III)-catalyzed cross-coupling reaction between indolyl nitrones and 2-methylidene cyclic carbonate as an allylating surrogate, resulting in the formation of C2-formylated carbazoles via tandem C-H allylation, [3 + 2] cycloaddition, aromatization, and benzylic oxidation. The synthetic utility of this protocol is highlighted by a variety of post-transformations of C2-formylated carbazoles.

Role of carbon fiber electrodes and carbonate electrolytes in electrochemical phenol oxidation.

In-situ chemical oxidation (ISCO) requires an injection of oxidants into a contaminated site. However, the oxidants decompose and react with contaminants during transport to the contaminated region, which causes oxidant over-consumption. In-situ oxidant generation can solve this problem, and electrochemical methods can be applied to achieve this. Electrochemical oxidation is highly dependent on electrode material type. In this study, we evaluated graphite and carbon fiber as candidates for electrochemical oxidant generation and phenol as the model compound. The carbon fiber anode oxidized the phenol more effectively than graphite, with removal proportional to the applied current. Carbonate electrolytes were more effective at oxidizing phenols than sulfate electrolytes. The faster carbon fiber anode phenol oxidation is due to its large surface area. Carbonate radicals in the carbonate electrolyte contribute to phenol oxidation as well as further intermediate oxidation. The carbon fiber cathode was not an effective phenol oxidizer even though it generated more hydrogen peroxide. This is because there was no catalyst to transform the hydrogen peroxide into hydroxyl radicals. Results indicate that electrochemical oxidation using carbon fiber is an effective method for treating phenol found in groundwater with high concentrations of (bi)carbonate.

Simultaneous oxidation and adsorption of arsenic by one-step fabrication of alum sludge and graphitic carbon nitride (g-C3N4).

The oxidation of trivalent arsenic (As(III)) to pentavalent arsenic (As(V)) is a common pretreatment to remove As(III) from the aqueous phase. The graphitic carbon nitride as a photocatalyst can transform As(III) to As(V), but the photocatalyst does not adsorb any species of arsenic. In this study, a new composite material to achieve the simultaneous oxidation and adsorption of arsenic was synthesized by co-pyrolyzing alum sludge and melamine. It was hypothesized that graphitic carbon nitride derived from melamine oxidizes As(III) to As(V) and pyrolyzed alum sludge provides strong adsorption sites for the oxidized As(V). The composites were characterized by X-ray diffraction, Brunauer-Emmett-Teller(BET) surface, scanning electron microscope, and X-ray photoelectron spectrometer. The composite material effectively converted As(III) to As(V) under the light, and the total arsenic concentration decreased in the aqueous phase via the adsorption of As(V). Speciation analysis of arsenic on the composite showed that both As(III) and As(V) species were present on the surface of adsorbent, from which desorption by mixing with deionized water was difficult. This new and green composite material can oxidize As(III) and adsorb arsenic simultaneously under the light, which can be used to treat arsenic-containing water.