Installation of fluorine into pharmaceutically relevant molecules plays a vital role in their properties of biology or medicinal chemistry. Direct difunctionalization of alkenes and 1,3-dienes to achieve fluorinated compounds through transition-metal catalysis is challenging, due to the facile β-H elimination from the Csp3‒[M] intermediate. Here we report a cobalt-catalyzed regioselective difluoroalkylarylation of both activated and unactivated alkenes with solid arylzinc pivalates and difluoroalkyl bromides through a cascade Csp3‒Csp3/Csp3‒Csp2 bond formation under mild reaction conditions. Indeed, a wide range of functional groups on difluoroalkyl bromides, olefins, 1,3-dienes as well as (hetero)arylzinc pivalates are well tolerated by the cobalt-catalyst, thus furnishing three-component coupling products in good yields and with high regio- and diastereoselectivity. Kinetic experiments comparing arylzinc pivalates and conventional arylzinc halides highlight the unique reactivity of these organozinc pivalates. Mechanistic studies strongly support that the reaction involves direct halogen atom abstraction via single electron transfer to difluoroalkyl bromides from the in situ formed cobalt(I) species, thus realizing a Co(I)/Co(II)/Co(III) catalytic cycle.
As et of rhenium-catalyzeda rylation-acyl cyclizations between (hetero)arylmagnesium halides and enol lactones through ac ascade C(sp 2 )ÀC(sp 2 )/C(sp 2 )ÀC(sp 2 )b ond formation under mild reaction conditions has been developed. Indeed, aw ide range of functional groups on both organomagnesium halides and enol lactones is well tolerated by the simple rhenium catalysis,t hus furnishing polyfunctionalized indenones in one-pot fashion and with complete control of the regioselectivity.M oreover,t his approacha lso provides as traightforwards ynthetic route to neolignan and (iso)pauciflorol F. Mechanistic studies demonstrated that the reaction involves asequence of syn-carborhenation and intramolecular nucleophilic addition.
Facile formation of carbon-heteroatom bonds is a long-standing objective in synthetic organic chemistry. However, direct cross-coupling with readily accessible alkenyl acetates via inert C‒O bond-cleavage for the carbon-heteroatom bond construction remains challenging. Here we report a practical preparation of stereoselective tri- and tetrasubstituted alkenyl silanes and stannanes by performing cobalt-catalyzed C‒O silylation and stannylation of alkenyl acetates using silylzinc pivalate and stannylzinc chloride as the nucleophiles. This protocol features a complete control of chemoselectivity, stereoselectivity, as well as excellent functional group compatibility. The resulting alkenyl silanes and stannanes show high reactivities in arylation and alkenylation by Hiyama and Stille reactions. The synthetic utility is further illustrated by the facile late-stage modifications of natural products and drug-like molecules. Mechanistic studies suggest that the reaction might involve a chelation-assisted oxidative insertion of cobalt species to C‒O bond. We anticipate that our findings should prove instrumental for potential applications of this technology to organic syntheses and drug discoveries in medicinal chemistry.
Pharmaceutical analysis, as the core curriculum of chemistry, chemical engineering, and pharmaceutical engineering, contains broad and in-depth knowledge that leads to massive learning and teaching loads. There are more than 100 analytical methods of medicines in this course. As such, this subject is a big challenge for both students and lecturers. A novel chemical structure teaching (CST) method was developed on the basis of our longterm teaching experience to cope with these challenges. It has been shown in practice that this CST method can significantly unload the stress of students and lecturers simultaneously. The survey about the improvement of students' interests was carried out and listed in the form of questionnaire. The outcome of CST indicates that it can help students to form abilities of critical and logical thinking, motivate them to discuss with their peers and lecturers, and eventually improve comprehensive abilities such as synthesizing information, thinking logically, and analyzing problems independently as well as the average score. Furthermore, CST can be beneficial for lecturers who teach other relevant curricula in chemical or pharmaceutical engineering to improve the teaching outcome, such as organic chemistry, spectrum analysis, pharmaceutical synthesis, and medicinal chemistry. This CST model can also help students cultivate a life-long learning ability as active learners from the cognitive perspective view.
A mild and simple method was developed to synthesize a highly efficient photocatalyst comprised of Ce-doped ZnO rods and optimal synthesis conditions were determined by testing samples with different Ce/ZnO molar ratios calcined at 500 °C for 3 hours via a one-step pyrolysis method. The photocatalytic activity was assessed by the degradation of a common dye pollutant found in wastewater, rhodamine B (RhB), using a sunlight simulator. The results showed that ZnO doped with 3% Ce exhibits the highest RhB degradation rate. To understand the crystal structure, elemental state, surface morphology and chemical composition, the photocatalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and inductively coupled plasma emission spectroscopy (ICP), respectively. The newly developed, robust, field-only surface integral method was employed to explore the relationship between the remarkable catalytic effect and the catalyst shape and porous microstructure. The computational results showed that the dipole-like field covers the entire surface of the rod-like Ce-doped ZnO photocatalyst and is present over the entire range of wavelengths considered. The optimum degradation conditions were determined by orthogonal tests and range analysis, including the concentration of RhB and catalyst, pH value and temperature. The results indicate that the pH value is the main influential factor in the photocatalytic degradation process and the optimal experimental conditions to achieve the maximum degradation rate of 97.66% in 2 hours are as follows: concentration (RhB) = 10 mg/L, concentration (catalyst) = 0.7 g/L, pH 9.0 and T = 50 °C. These optimum conditions supply a helpful reference for large-scale wastewater degradation containing the common water contaminant RhB.
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