A highly enantioselective [3+3] aza-cyclization of α, β-unsaturated aldehydes with 3-aminobenzofuran promoted by diphenylperhydroindolinol silyl ether has been described, which afforded benzofuran derivatives in high yields (up to 93%), diastereoselectivities ( dr>20∶1) and enantioselectivities (86%~>99% ee). This method also enabled to obtain benzofuran derivatives in gram scale-up.

A novel and efficient synthesis of γ-alkynyl ketones by the direct nucleophilic substitution of propargyl alcohols with enoxysilanes in the presence of a catalytic amount of p-toluenesulfonic acid monohydrate, has been developed. The reactions can be performed in an undried solvent under an air atmosphere to obtain the desired products in good yields.

A mild method for the conversion of alkyl iodides to alcohols was developed. The transformation was promoted by tris(trimethylsilyl)silane/O₂ and accelerated by photoredox catalysis under visible light irradiation conditions. Various alkyl iodides, including primary, secondary and tertiary iodides, can be smoothly converted to the corresponding alcohols in 38%~99% yields.

The introduction of methyl group into aromatic compounds is a valuable transformation. A large number of known methods use organohalides as the starting materials. However, those methods require pre-synthesized methyl metal reagents or toxic methyl electrophiles. Herein, a palladium-catalyzed reductive coupling reaction between aryl bromides and trimethylsilyl-diazomethane is developed, and the following desilicification process can afford the methylated products. This transformation has broad functional group tolerance and allows methylation of (hetero)aryl halides in moderate to good yields. Thus, it has the potential to be an attractive approach for methylation of organic. In addition, this reductive coupling can also serve as an efficient way for the introduction of silylmethyl group.

Amines are important intermediates in organic synthesis. The hydrosilylation of imines provides a convenient method for the synthesis of amines. Transition metal and main group catalysts have been widely applied in the hydrosilylation of imines. However, it would be more practical to use simpler reaction conditions to realize such reactions. In this paper, a fast hydrosilylation of aldimine was realized by using cheap t-BuOK as the promoter, providing an efficient method for the synthesis of amines in high yield. This reaction features rapid reaction, facile conditions, and robust practicability.

Chlorosulfonation of acetanilide was accomplished within 10 min in up to 96% yield via a highly thermoconductive and corrosion-resistant dual-temperature-zone silicon carbide microchannel reactor. The yield of pilot production was up to 92%. In the first stage, low reaction temperature (40℃) was employed to effect a high sulfonation selectivity at the para position of acetanilide. In the second stage, a higher reaction temperature (100℃) led to a faster formation of chlorosulfonation product. To illustrate the application of this reaction, sulfasalazine with antimicrobial and anti-inflammatory activities was synthesized in total yield of 75% via chlorosulfonation, sulfamide formation, hydrolysis under base conditions, diazotization and coupling with salicylic acid. The two-step continuous reaction helped to solve the problems in batch reactor, such as low temperature leading to slow reaction and high temperature resulting byproducts and/or temperature runaway, the safety concern aroused by heat accumulation, and the polution caused by the use of large excess of chlorosulfonic acid in batch production. The above research provides technical support for the large-scale industrial production of p-acetylaminobenzenesulfonyl chloride and its sulfonamides.

The selective aminocarbonylation of vicinal diketones using carbamoylsilane as an amide source affords β-keto-α-siloxyamide derivatives in 62%~90% yields under mild conditions without using any oxidants and catalysts. The steric hindrance, which is both from the groups of vicinal diketones and the carbamoylsilanes, affects reaction selectivity on two carbonyl groups. The methoxymethyl or benzyl used as an amino protecting group, can be easily converted into hydrogen atom leading to β-keto-α-hydroxy secondary or primary amides. The simple procedure allows the preparation of various β-keto-α-hydroxy amide derivatives including primary, secondary and tertiary β-keto-α-hydroxy amide derivatives. The reaction has the advantages of mild conditions, less by-products, high selectivity, good yield and simple post-treatment, and it is a new method for the efficient preparation of β-keto-α-hydroxyamides.

Using di-tert-butyl peroxide (DTBP) as oxidant, chloroform or carbon tetrachloride as trichloromethyl radical source and reaction solvent, enol silyl ethers derived from aryl ketone was transferred to β,β-dichloro-α,β-unsaturated ketone by trichloromethyl radical addition/elimination. The conditions are mild with avoiding the use of metal catalysts, and the enol silyl ethers substrate has good universality.

Allylation reactions of trifluoromethylated acylhydrazones with allyltrimethylsilane or pinacolyl allylboronate were found to proceed smoothly in the presence of Lewis acid to afford a series of trifluoromethylated homoallylic N-acylhydrazines with high yields. The results showed that the activity of pinacolyl allylboronate was higher than that of allyltrimethylsilane in allylation of trifluoromethylated acylhydrazones.

Cobalt is abound in the earth and has advantages of low cost and low toxicity. Cobalt complexes have been widely applied as catalysts in numerous catalytic organic reactions, in which the complexes show excellent catalytic performance and have been recognized as a very important research field. The recent progress in the application of cobalt complexes in the catalytic hydrosilylation of alkenes, alkynes, carbonyl compounds and other unsaturated double bond is summarized. Furthermore, the deficiencies of the catalysts have been discussed. At last, the future development and prospects of these complexes as catalysts are also proposed.

Allylsilanes have emerged as synthetically useful intermediates that can undergo a variety of chemical transformations and have been found versatile applications in C-C bond construction as well as in preparation of complex molecules. Exploration on the stereoselective route to functionalized allylsilanes is of great significance for the development of organic synthetic methodology. An efficient pathway to a series of novel alkoxy-substituted homoiodio-allylsilanes via the Julia olefination of silylmethyl cyclopropyl carbinols was described. Carbinols derived from cyclopropyl aryl ketone were evidenced to be superiorer in controlling the stereoselectivity of the products than the alkyl equivalents.

3-Hydroxy-3-heterocyclebutyl amide derivatives were directly synthesized in 56%~85% yields by nucleophilic addition of various carbamoylsilanes to oxetane-3-one or thietane-3-one in toluene under mild and catalyst-free conditions. This method will provide an efficient route for the synthesis of drugs containing four-membered heterocycles which have not additional stereocentres. The procedure can prepare 3-hydroxy-3-heterocyclebutyl tertiary, secondary and primary amides as well as having a stereocentre connecting with nitrogen atom by selecting different carbamoylsilanes. A comparison of the results obtained from reaction of various carbamoylsilanes indicated that the size of group on the amide group was an important factor in the addition reaction, which influenced on both the reaction time and yields. The reaction has the advantages of mild conditions, less by-products, good yield and simple post-treatment, and is a new method for the efficient preparation of 3-hydroxy-3-heterocycle butylamides.

Organosilanes have been widely applied in synthetic chemistry, pharmaceuticals, agrochemicals, and materials due to the special properties. Several synthetic strategies including nucleophilic substitution, hydrosilylation of alkene, and C-H silylation have been developed. In recent years, significant progress has advanced in the cross-coupling of C-Si bond for the synthesis of organosilanes, especially in the break-through of the cross-coupling of C(sp³)-Si bond. It has become one of the hottest issues in synthetic chemistry. The recent progress on the cross-coupling of C-Si bond by using silyl reagents is summarized. The application of silyl reagents in cross-coupling for C-Si bond formation including silyl boranes, organosilyl magnesium, organosilyl zinc, unasymetric disilanes, organosilyl aluminum and organosilyl lithium reagents is mainly discussed.

Organosilicon compounds play an important role in pharmaceutical chemistry, material science and organic synthesis. Transition-metal-catalyzed direct silylation of C-H bond, as one of the most concise and efficient methods for the synthesis of organosilanes, has developed rapidly in recent years. In this paper, the recent advance in transition-metal-catalyzed silylation of C-H bonds since 2015 is mainly reviewed.

The chemistry of frustrated Lewis pairs (FLPs) is among the challenging frontiers of synthetic chemistry, which provides a powerful approach for metal-free catalytic hyrogenations and Piers-type hydrosilylations. In recent years, a significant progress has been made in this field. However, the deveopment of asymmetric reactions is still sluggish. The lacks of highly effective and enantioselective chiral FLP catalysts represent the key issue. C₂-symmetric 1,1'-spirobiindane is one privileged framework in chiral ligands and catalysts. On the basis of chiral binaphthyl diene-derived frustrated Lewis pairs (FLPs) developed by our group, in this work, we designed and synthesized a novel class of chiral spiro dienes, which could further react with Piers' borane via the hydroboration reaction to generate chiral boranes in situ. With the combination of chiral borane and tri-tert-butylphosphine as an FLP catalyst, an asymmetric Piers-type hydrosilylation of simple ketones was successfully realized to give the desired secondary alcohols with up to 90% ee.

A highly chemo-, regio-, and stereo-selective cobalt-catalyzed dehydrogenative silylation of vinylarenes was described. The imidazoline iminopyridine cobalt complex could promote this reaction effectively and improve the chemoselectivity dramatically. This protocol used earth-abundant transition metal, readily available alkenes and hydrosilanes to construct valuable vinylsilanes. The reaction could be carried out in gramscale and the proposed mechanism was also described.

The selective reduction of carbonyl group with organosilane as reducing agent was studied with methanol as a solvent under the action of 2.5 mol% C₆H₅BF₃K and 2.2 epuiv. (EtO)₃SiH. The target products were obtained in medium to high yield. This method shows good selectivity and provides a new method for carbonyl reduction.

A convenient method for improving the conversion and selectivity of aniline to azoxybenzene by adjusting the ratio of silicon to titanium of TS-1 is reported. Over TS-1 (80), aryl anilines are transformed into the corresponding azoxybenzenes in good yields with H₂O₂ as the oxidant. The effect of different reaction parameters like molar ratio of H₂O₂ to aniline, solvent and the activity in catalyst recycling has been studied.

Aerogel is a kind of gel materials, of which the fluid phase is gas. Aerogel has the characteristics of low density and high porosity, and has a wide application prospects. In this work, a rapid solvents exchange method was developed, and using in-situ secondary extraction, rapid solvents exchange in aerogel preparation was achieved through the miscibility and immiscibility of ethanol-dichloromethane-water. Combined with hydrophobic treatment and vacuum drying, hydrophobic silica aerogel was obtained. The aerogel had a low density and a contact angle with water of 155.8°. The aerogel can load various organic fluorescent probe dyes, which can effectively avoid the fluorescence quenching caused by the aggregation of the probe molecules, which it will expand the practical application range of the organic fluorescent probes in wider fields.

α-(N-Sulfonyl)amino amide derivatives are directly synthesized in 71%~89% yields by the reaction of carbamoylsilanes with various N-sulfonylimines in benzene under catalyst-free conditions. The procedure can prepare both tertiary and secondary α-amino amides. A comparison of the results obtained from the N-sulfonylimines containing the variety of alkyl, aryl and heterocyclic ring indicated that the electronic effect was an important factor in the addition reaction, which influenced on the rate and yields of the reaction. The new method is simple and mild procedure, no catalysts conditions, less byproducts and good yields for the preparation of α-aminoamides.

A gold(I)-catalyzed 1,2-silyl migration on 1,8-di-substituted naphthalene rings was realized by synergistic effect of Lewis acid and water. High yields were achieved under relatively mild conditions.