We report a copper-catalyzed selective 1,2-phosphonoazidation of conjugated dienes. This three-component reaction is achieved by using readily available P(O)-H compounds and bench-stable NaN3. Salient features of this strategy include its mild reaction conditions, broad functional group tolerance, and high chemoselectivity and regioselectivity. Moreover, the compatibility with the late-stage functionalization of drug molecules, the potential for scalable production, and the feasibility of further modifications of the products underscore the practical utility of this protocol in synthetic applications.
A visible-light-induced glycoarylation of activated olefins has been accomplished. Glycosyl radicals are generated via radical transfer strategies between (TMS)3SiOH and glycosyl bromides. Subsequent radical translocation and rapid 1,4-aryl migration form ß-sugar amide derivatives, and eight types of sugars are compatible with this reaction. Further, the cascade reaction produced a quaternary carbon center with good functional group adaptability and high regioselectivity in mild conditions.
Construction of C(sp2)-C(sp3) bonds via regioselective coupling of C(sp2)-H/C(sp3)-H bonds is challenging due to the low reactivity and regioselectivity of C-H bonds. Here, a novel photoinduced Ru/photocatalyst-cocatalyzed regioselective cross-dehydrogenative coupling of dual remote C-H bonds, including inert γ-C(sp3)-H bonds in amides and meta-C(sp2)-H bonds in arenes, to construct meta-alkylated arenes has been accomplished. This metallaphotoredox-enabled site-selective coupling between remote inert C(sp3)-H bonds and meta-C(sp2)-H bonds is characterized by its unique site-selectivity, redox-neutral conditions, broad substrate scope and wide use of late-stage functionalization of bioactive molecules. Moreover, this reaction represents a novel case of regioselective cross-dehydrogenative coupling of unactivated alkanes and arenes via a new catalytic process and provides a new strategy for meta-functionalized arenes under mild reaction conditions. Density functional theory (DFT) calculations and control experiments explained the site-selectivity and the detailed mechanism of this reaction.
Herein, we describe the copper-catalyzed arylalkylation of activated alkenes via hydrogen-atom transfer and aryl migration strategy. The reaction was carried out through a radical-mediated continuous migration pathway using N-fluorosulfonamides as the alkyl source. The primary, secondary, and tertiary alkyl radicals formed by intramolecular hydrogen-atom transfer proceeded smoothly. This methodology is an efficient approach for the synthesis of various amide derivatives possessing a quaternary carbon center with good yields and high regioselectivity.
We report a novel Ru-catalyzed regioselective alkylarylation of vinylarenes with alkyl halides and arenes via meta-C(sp2)-H bond functionalization to construct 1,1-diarylalkanes that generally show bioactivity. In this transformation, a wide spectrum of primary, secondary, and tertiary alkyl halides and electronically varied arenes was well-tolerated. This reaction is characterized by its exquisite regioselectivity of vinylarenes, unique meta-C(sp2)-H selectivity, and redox-neutral conditions. The mechanism presented was supported by radical probes and kinetic isotope effect studies.
A novel dehydrogenative coupling reaction of N-fluorocarboxamides with polyfluoroarenes forming C(sp2)-C(sp3) bonds enabled by copper catalysis has been accomplished. N-Fluorocarboxamides are postulated to undergo copper-mediated dehydrogenative cross-coupling reaction with electron-deficient polyfluoroarenes via a radical pathway. Benzylic C-H bonds and aliphatic C-H bonds in N-fluorocarboxamides could proceed smoothly and demonstrated excellent regioselectivity. The detailed mechanism presented is supported by control experiments and density functional theory calculations.
High-frequency sampling was conducted at the outlet of Guangxi Bishuiyan karst subterranean river using an automatic sampler during the rainfall events. The hydrochemical drymanic variation characteristics of trace metals (Cu, Pb, Zn, Cd) at the outlet of Guangxi Bishuiyan karst subterranean river were analyzed, and the sources of the trace metals in the subterranean river as well as their response to rainfall were explored. The results showed that the rainfall provoked a sharp decrease in the major elements (Ca²âº, Mg²âº, HCO3â», etc.) due to dilution and precipitation, while it also caused an increase in the concentrations of dissolved metals including Al, Mn, Cu, Zn and Cd, due to water-rock reaction, sediment remobilization, and soil erosion. The water-rock reaction was more sensitive to rainfall than the others, while the sediment remobilization and soil erosion took the main responsibility for the chemical change of the heavy metals. The curves of the heavy metal concentrations presented multiple peaks, of which the maximum was reached at 9 hours later after the largest precipitation. Different metal sources and the double-inlet structure of the subterranean river were supposed to be the reasons for the formation of multiple peaks. During the monitoring period, the average speed of the solute in the river reached about 0.47 km · h⻹, indicating fast migration of the pollutants. Therefore, monitoring the chemical dynamics of the karst subterranean river, mastering the sources and migration characteristics of trace metal components have great significance for the subterranean river environment pollution treatment.
Metals, Heavy/analysis , Rain , Rivers/chemistry , Water Pollutants/analysis , China , Environmental Monitoring , Geologic Sediments , Soil , Trace Elements/analysis , Water
