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The tandem decarboxylative condensation-dimerization reaction of l-proline with 2,5-cyclohexadienones including p-quinone monoacetals, p-quinol ethers, and p-quinols is reported to provide a concise and rapid synthesis of octahydro-dipyrroloquinoline compounds. The reaction features the use of cost-effective and readily available starting materials, high efficiency, metal-free and green reaction conditions. The reaction is applied to the synthesis of incargranine B aglycone. The discovery of this reaction may suggest a biosynthetic pathway from 2,5-cyclohexadienones and proline for natural ingredients containing pyrroloquinoline moieties.

The three-component reactions of α-amino acids, p-quinone monoacetals (or p-quinol ethers), and diarylphosphine oxides have been developed for the synthesis of 3-(diarylphosphinyl) anilides and N-aryl-2-diarylphosphinylpyrrolidines. The transformations may involve the in situ generation of conjugated azomethine ylides or 2-azaallyl anion species from the reaction of α-amino acids and p-quinone monoacetals, which are further trapped by diarylphosphine oxides.

2,4,5-Trifluorobromobenzene is a valuable synthetic intermediate with important applications in pharmaceutical industry. We report a continuous microflow process for the synthesis of 2,4,5-trifluorobromobenzene via Gattermann reaction in this paper. The microflow system is easily assembled by a simple T-micromixer, microchannel reactors and several pumps. The use of this system facilitated the diazotization reaction of 2,4,5-trifluoroaniline with HBr and NaNO 2 to produce the thermally unstable 2,4,5-trifluorophenyl diazonium salts in seconds, which then react with HBr at the catalysis of copper powder to obtain 2,4,5-trifluorobromobenzene. The aqueous HBr containing copper powder was added and stirred for 30 min at 70 °C in the stirred vessel. And then, the CuBr in situ was given and performed a quench-type reaction as catalyst. The influence of the reaction parameters on the diazotization reaction steps was examined and discussed in microreactors. The microflow system had the capacity to promote efficient mass- and heat-transfer and shorten the reaction time. On this basis, the kilogram-scale production of 2,4,5-trifluorobromobenzene was realized in a self-made scale-up microreactor by numbering-up of micromixers and microchannels.

A less expensive and more environmentally friendly Zn(OTf)2-catalyzed dehydrative coupling reaction of propargyl alcohols with diarylphosphine oxides is reported. The reaction takes place under mild and solvent free conditions, and features a high regioselectivity to provide an effective method for the synthesis of some diarylphosphinyl allenes in moderate to high yields.

2,4,5-Trifluorobenzoic acid is a valuable synthetic intermediate with important application in pharmaceutical industry and material science. In this paper, we report a facile continuous microflow process for the synthesis of 2,4,5-trifluorobenzoic acid via the generation of an unstable aryl-Grignard reagent followed by its reaction with gaseous CO2. The microflow system is easily assembled by a simple T-micromixer, a commercial available falling film microreactor, tube microreactor and several pumps. The use of a composed T-micromixer and tube microreactor facilitates the Grignard exchange reaction of 2,4,5-trifluorobromobenzene with ethylmagnesium bromide producing 2,4,5-trifluorophenylmagnesium bromide almost in quantitative yield, and the use of the falling film microreactor enables a highly efficient gas–liquid reaction of the resultant Grignard reagent with CO2 under an atmosphere pressure, which ultimately gave the product 2,4,5-trifluorobenzoic acid in high yield with high purity after a simple and extractive workup. The influence of reaction parameters on the two steps in microreactors was discussed.

The amino-modified mesoporous material SBA-15 (NH2-SBA-15) was prepared via co-condensation of tetraethylorthosilicate with 3-aminopropyltriethoxysilane in the presence of an amphiphilic triblock copolymer as a pore-directing agent under acidic conditions. The SBA-15-supported Cu Schiff-base complex (Cu-SBA-15) was then synthesized by condensation of salicylaldehyde with NH2-SBA-15, followed by the addition of a solution of Cu(NO3)2. The supported complex was systematically characterized by elemental analysis, inductive coupled high frequency plasma atomic emission spectrometry, powder X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, field scanning electron microscopy, transmission electron microscopy, N2 absorption-desorption, and thermo gravimetric analysis, and was used as the catalyst for the selective oxidation of styrene to benzaldehyde. The influence of the reaction parameters was assessed. The maximum conversion of styrene was 84.4% and the selectivity for benzaldehyde was 83.9%, when the reaction was conducted with a 2:1 molar ratio of H2O2:styrene in the presence of 3.8 wt% catalyst at 100 °C for 8 h. The TOF was 261.1 h−1, and the catalyst could be used three times without significant loss of activity. The uniformly sized pore channels, high specific surface area, and well-distributed active centers of the catalyst may contribute to the high activity.

Present work demonstrated the facile preparation of silica microspheres with various structures (solid, hollow, hollow with a hole and filbert-like solid). These were prepared by first forming monodisperse silica sol droplets in a simple microfluidic device, followed by extracting the solvent from the droplets in an extractant or at the interface between the extractant and liquid paraffin at different conditions. The effect of different extractants and extracting temperature was investigated. The products were characterized by optical microscope and scanning electron microscope. Extraction in fatty acid methyl ester (FAME) at room temperature led to formation of solid silica microspheres, while extraction at the interface between FAME and liquid paraffin at 60 °C resulted in formation of hollow silica microspheres. Use of mixture of castor oil (CO) and dimethyl carbonate (DMC) as extractant resulted in formation of hollow silica microspheres with a hole on the surface, whereas increase in the DMC content in extracting medium led to formation of filbert-like silica solid microspheres. Change in size of cavity and hole was studied by changing the extracting temperature. The formation process and mechanism of these silica microspheres are proposed based on the diffusion rate. The relationship between the size of the microspheres and the state of the droplet at the interface is correlated.

The nucleophilic addition of sodium azide to 1,2-allenyl esters can generate vinyl azides in excellent yields with excellent regio- and stereoselectivities. Moreover, pyrroles are synthesized using 1-allyllic 1,2-allenyl esters as substrates in t-BuOH at 65 degrees C. The sequential reaction for pyrroles is developed on the basis of a novel domino process involving nucleophilic addition, cycloaddition, denitrogenation, and aromatization.

The reaction of H-phosphinates and secondary phosphine oxides with amines and alcohols proceeds highly stereospecifically to give the corresponding coupling products with inversion of configuration at the phosphorus center under the Atherton-Todd reaction conditions. This finding leads to the establishment of a general and efficient method for the synthesis of a variety of optically active organophosphorus acid derivatives from the easily available chiral H-phosphinates and secondary phosphine oxides.

A general and efficient method for the preparation of optically active Z1Z2P(O)Cl from the easily prepared optically active H-phosphinates and H-phosphine oxides was reported. H-Phosphinates and H-phosphine oxides react stereospecifically with CuCl2 to produce the corresponding optically active Z1Z2P(O)Cl with retention of configuration at the phosphorus center. Optically active Z1Z2P(O)Cl reacts easily with a variety of nucleophiles to produce other chiral organophosphorus acid derivatives with inversion of configuration at phosphorus.

A novel reaction pathway of 2,3-allenoates with an electrophile (TsNBr2) in the presence of K2CO3 to produce (1E,2E)-3-bromo-4-oxo-N'-tosyl-2-alkenoxylimidic acid ethyl esters is reported. The reaction proceeds in a highly stereoselective fashion. A plausible mechanism to rationalize this reaction is also proposed.

Trimethylphosphine efficiently catalyzed the dimerization reaction of vinylphosphorus compounds to selectively afford the linear non-branched tail-to-tail β,β-dimerization dimers via umpolung of the substrates.