In the past two decades, organosilicon compounds bearing silicon-stereogenic centers have attracted extensive attention in the fields of organic synthesis, materials, and drug design. However, the expansion of organosilicon compounds in these fields has been greatly restricted by limited source of organosilicon compounds. Therefore, the development of highly efficient and selective asymmetric catalytic methods to obtain chiral organosilicon compounds with silicon-stereogenic centers is a challenging task that needs to be solved urgently. The latest research progress on new catalytic reaction systems for asymmetric synthesis of silicon-stereogenic center containing organosilanes since 2011 is mainly summarized.

Organosilicon compounds are important monomers and useful organic molecules in many materials, and are widely used synthetic intermediates in chemical synthesis. Therefore, people have been working hard to develop new methods to construct silicon containing chemical bond, especially C—Si bonds. Since Sakurai and Imai reported the first palladium catalyzed cycloaddition reaction of silcyclobutane with acetylene in 1975, transition metal catalyzed silyl annulation has been developed rapidly. With the rapid development of free radical reactions, researchers have expanded them to the annulation reaction between organic silicon molecules, ushering in new developments in the annulation reaction of silicon. The transition metal catalyzed silylative annualtion reaction, free radical initiated silylative annualtion reaction, and C^＋ ion initiated silylative annualtion reaction are mainly discussed. Finally, a summary of the current research progress is described.

Silahydrocarbons are often encountered in pharmaceuticals and material chemistry. In comparison with all-carbon parent compounds, carbon/silicon switch generally endows the corresponding compounds with different biological activity and physical-chemical properties. In this review, the methods and strategies of synthesis of organosilanes by photoredox in recent years are reviewed, and the corresponding reaction mechanisms and limitations are discussed.

A copper-catalyzed mono-lateral protosilylation of dialkynylphosphine oxides for the synthesis of β-silyl substituted vinylphosphine oxides is described. Various (hetero)aryl and alkyl-substituted diynes afforded the corresponding products in moderate and high yields with high chemoselectivity. An alternative alkynyl functional group of products could also be further derived.

The initiation polymerization property of (meth)acrylates by using the silylene/organoaluminum Lewis pair (LP) system is studied. Four silylenes L(Ph₂P)Si (Si-1, L=PhC(N^tBu)₂), L[4-MeC₆H₄(Ph₂P)N]Si (Si-2), L[2,6-ⁱPr₂C₆H₃(1,5- C₈H₁₄B)N]Si (Si-3), and L(LSi)Si (Si-4) as the Lewis base (LB) were synthesized, together with six organoaluminums Al(C₆F₅)₃, AlMe(BHT)₂, AlⁱBu(BHT)₂, AlⁱBu₂(BHT), AlⁱBu(BHT^*)₂, and AlⁱBu₂(BHT^*) (BHT=2,6-^tBu₂-4-MeC₆H₂O and BHT^*=2,4,6-^tBu₃C₆H₂O) as the Lewis acid (LA). Si-1/organoaluminum and Si-4/organoaluminum LP systems all enable to initiate the complete methacrylate (MMA) polymerization, achieving turnover of frequency (TOF) activities in the range of 50~400 h^-1 with PMMA M_n of 82000~271000 and Đ of 1.11~1.81. Neither Si-2/organoaluminum or Si-3/organoaluminum was active. The Si-1/Al(C₆F₅)₃ displayed poor reactivity on n-butyl acrylate (nBA) and 2-ethylhexyl acrylate (EHA). However, the Si-1/other organoaluminums exhibited both complete nBA and EHA polymerizations. For nBA, the TOFs were obtained by 4.8×10⁴~14.4×10⁴ h^-1, in which the PnBAs were produced with M_n 100000~179000 and Đ 1.08~1.59. For EHA, the TOFs were up to 14.4×10⁴~36.0×10⁴ h^-1, where the PEHAs were yielded with M_n 81000~240000 and Đ 1.12~1.95. The probable polymerization mechanism with the silylene/organoaluminum LP system is investigated.

Regioselectivity adjustment is one of the key research fields in organic chemistry, and electronic effect is the key factor for adjustment. In this work, density functional theory (DFT) calculation was carried out to investigate how electronic effect of substituent affects regioselectivity in the reductive elimination step. Palladium-catalyzed annulation of silacyclo- butanes and 2-iodobiarenes was selected as model reaction, and detailed reaction mechanism is illustrated. The results shows that the reaction undergoes Pd—I bond oxidative addition, concerted metalation deprotonation (CMD), Pd—Si bond oxidative addition, and reductive elimination process to synthesize eight-membered silacycles, and C—Si bond reductive elimination is the rate determining step. Study of electronic effect in Pd(IV) reductive elimination transition state shows that when asymmetrically substituted 2-iodobyphenyl is used as substrate, electron density of aromatic ring is the main factor to control regioselectivity. Groups with higher electron density have higher priority for reductive elimination, and this is in accordance with electron flow in this elementary reaction.

Hydrosilylation of carbon dioxide (CO₂) is one of the most significant sustainable approaches for utilizing CO₂ as a C1 feedstock. This approach enables the conversion of CO₂ to value-added chemicals at various oxidation levels, such as formate, formaldehyde, methanol, or methane. Additionally, the formylation and/or alkylation of the N—H bonds of amines can also be achieved in certain catalytic systems with CO₂ and hydrosilanes. Currently, remarkable progress has been made in the field of CO₂ hydrosilylation. This focused review mainly describes advances in the design and catalytic performance of leading catalytic systems reported in the past three years, including noble transition metal catalysis, nonprecious transition metal catalysis, rare-earth metal catalysis, main-group metal catalysis, and metal-free catalysis. Moreover, current bottlenecks and perspectives of this field are also discussed.

Due to the widespread application of various organosilicon compounds in material science, electronic devices and pharmaceutical research, it is of great significance to develop green and efficient synthetic methods for diverse silicon-con- taining molecules. Silacyclobutane is an important kind of small-membered rings, which exhibits unique reactivities under transition metal catalysis to cleave the C—Si bond driven by the inherent ring strain and Lewis acidity. The resulting Si—M species can then be transformed into various organosilicon compounds. Herein, the recent advances of Pd, Rh, and Ni-catalyzed C—Si bond cleavage reactions of silacyclobutanes are summarized in detail, and the mechanism and development tendency of such reactions are briefly discussed.

Bromodifluoromethyl trimethylsilane (TMSCF₂Br) has proved to be an important difluoromethyl(alkyl)ation reagent that is widely applied in organic synthesis over the past decade, since it was used as a difluorocarbene precursor in 2011. This review aims to provide a briefly summary for the synthesis of TMSCF₂Br, and to introduce the recent advances in the applications of TMSCF₂Br as a difluorocarbene or trimethylsilyldifluoromethyl radical precursor for developing various difluoromethyl(alkyl)ations of different kinds of substrates. Meanwhile, the activation ways of TMSCF₂Br and the possible mechanism, as well as its advantages and disadvantages in each kind of reactions are detailedly disccussed, which might provide some references and inspiration for researchers engaged in organic synthesis and organic fluorine chemistry.

Organosilicons are widely used in many chemistry related fields. Given its important role, the chemical syntheses of organosilicon compounds have received considerable attention. Due to outstanding advantages in cost and environmental friendliness, transition-metal-free C—Si bond formation has been widely studied in the past decades and has been emerged as an important alternative to transition-metal-catalyzed C—Si cross-coupling. In this review, the recent developed methods of carbon-silicon bond formation under transition-metal-free conditions are summarized. The discussion is organized according to catalysts (acid catalysis, base catalysis, and radical initiation) and the types of C—Si bonds that formed. In addition, mechanistic discussions of representative reactions and a prospect for future development in this field are also briefly included.

Organosilicon compounds have been widely applied in synthetic chemistry, medicinal chemistry, polymer chemistry, organic photoelectric materials and other fields due to their unique properties. The silylation of unsaturated compounds represents one of the most important approaches for the synthesis of organosilicon compounds, which has attracted the intensive attention of chemists, and a great success has been achieved. As a unique non-metallic Lewis acid, B(C₆F₅)₃-catalyzed silylation of unsaturated compounds has made a significant progress in recent years. This subject and the corresponding mechanism are demonstrated.

The Hiyama coupling reaction has emerged as a wildly used method for the construction of C—C bonds, especially in the fields of aryl-aryl and aryl-alkenyl coupling reactions. In general, this protocol highly relies on reactive but unstable silicon reagents such as R—SiF₃ and R—Si(OMe)₃. The development of Hiyama coupling reaction involving stable organosilanes is in high demand. In this manuscript, a palladium-catalyzed cross-coupling reaction of aryl vinylsilanes and aryl halides is reported, leading to the formation of Ar—Ar bonds. The reaction has shown good functional group compatibility and offered convenient access to biaryl compounds.

Organosilicon products have become an indispensable part of our lives today. Catalytic hydrosilylation reaction is one of the important methods for preparing organosilicon chemicals and materials. The research and development of inexpensive and excellent catalysts have received extensive attention. At present, the research on catalytic hydrosilylation mainly focuses on exploring the catalytic properties of new noble metal and non-precious metal complexes. However, due to the high cost of noble metals and the low catalytic activity of non-noble metal complexes, photocatalysis is an environmentally friendly and safe method. Catalytic methods and photocatalytic hydrosilylation reactions have received much attention. In this paper, the research progress of photocatalytic hydrosilylation in recent years is introduced.

A novel photoredox/Lewis base dual-catalytic defluorinative silylation reaction of trifluoromethylsubstituted alkenes for the synthesis of gem-difluoroallylsilanes is reported, where silylboranes are employed as the silyl donor reagents. The protocol proceeds via the catalytic activation of Si—B bond by a Lewis base quinuclidine and the formation of silyl radical, making it easy to scale up. It features mild and green reaction conditions, simple reaction system, broad substrate scope and good functional group compatibility. Furthermore, the potential of this class of building blocks in the construction of various gem-difluoromethyl-containing structures has been also demostrated.

A nickel-catalyzed [4＋2] cyclization reaction between benzosilacyclobutenes and acylsilanes for the synthesis of cyclic bissilanes is reported. The mild reaction showes good substrate scope and the products can be transformed to monoaclohols or diols via one-step down-stream transformations.

Owing to its unique structure and properties, silicon-stereogenic silanes have displayed valuable application prospects in the fields of organic synthesis, functional materials and biomedicine, and have received extensive attention from chemists. In recent years, methods for the construction of silicon-stereogenic center have been rapidly developed, especially the use of transition metal catalysis to conduct the desymmetrization of prochiral silanes. Among them, asymmetric catalytic Si—H/X—H dehydrogenative coupling (Si-CADC) using dihydrosilane as the substrate has become an important approach and key technology for the construction of silicon-stereogenic center, because of its advantages of high efficiency, high atomic economy, good structural diversity and high enantioselectivity. According to the different reaction categorie and products, this review will mainly summarize and discuss in three stages: (1) asymmetric dehydrogenative coupling tandem strategy to construct tetrasubstituted silicon-stereogenic silanes, (2) intramolecular Si—H/C—H dehydrogenative coupling to construct cyclic silicon-stereogenic monohydrosilanes, and (3) intermolecular Si—H/X—H dehydrogenative coupling to construct a variety of ayclic silicon-stereogenic silanes.

Transition metal-catalyzed hydrosilylation of alkene has become one of the most important and fundamental homogeneous catalytic reactions, however, such reactions still face the problems of massive consumption of precious metal catalysts in industrial applications. Iron-series metals are abundant in the Earth's crust, cheap, easy to obtain, and biocompatible. Compared with precious metals such as platinum, iron-series metals have many advantages as catalysts, but there are still large gaps in catalytic hydrosilylation of alkene and tertiary silanes, especially involving industrial applications of silicones, and cannot replace precious metal catalysts for large-scale industrial production at current stage. The development of new iron-series metal catalysts for the efficient and highly selective hydrosilylation reaction of alkene with tertiary silanes and the in-depth discovery of the regulations on activity and selectivity of the catalysts are of great research value and have become a hot research area with a series of important progresses. The research progress in the hydrosilylation of olefins and tertiary silanes catalyzed by iron-series metals is systematically reviewed, the challenges faced in this field are discussed and the future development direction of this field is also prospected. Only the reactions promoted by homogeneous catalysts are introduced.

The last decade has witnessed the great development of SuFEx reactions. The synthetic value of SuFEx reactions in the preparation of small molecules and polymers is reviewed. The paper is arranged based on the types of substrates and the possible direction of the reaction is discussed.

β-Keto sulfones are an important group of sulfur-containing compounds and intermediates for organic synthesis, which are widely used in the construction of natural products and various important organic compounds. A method for the rapid synthesis of β-keto sulfones catalyzed by copper bromide from enol silyl ether and sodium arylsulfinates is developed, which has the advantages of simple operation, mild conditions and short reaction time.

A series of silane-bridged tetraphenylethene (TPE)-oligothiophene derivatives were synthesized. The silane substituents varied from methyl to phenyl groups, while the number of thiophene units in the oligothiophene segment was 1 to 3. The solid-state luminescence properties of the molecules were regulated by steric hindrance and electronic effects. Phenyl substituted silane-bridged bithiophene (BT)-TPE molecules exhibited up to 64.5% solid-state luminescence. Molecules containing 1 or 2 thiophene units exhibited fluorescence properties similar to TPE in both solid and liquid states, while the emission of molecules containing 3 thiophene units mainly came from terthiophene (TT) with luminescence efficiencies of 1.4% and 14% in liquid and aggregated states, respectively. The aggregate of phenyl substituted silane-bridged TT-TPE molecules exhibited potential for detecting nitro explosives and anti-counterfeiting applications.

Chiral allylsilanes, a versatile linchpin, are widely used in the area of asymmetric synthesis. Therefore, the development of efficient methodologies for the preparation of the enantioenriched allylsilanes has attracted great attention. Significant advances have been made in the catalytic enantioselective preparation of chiral allylsilanes by virtue of the rapid developments in asymmetric catalysis. The advances in the construction of chiral allylsilanes and their synthetic applications are summarized.

Carboxylic acids play important roles in basic life processes within organisms, and are powerful building blocks in the field of organic synthesis. Therefore, natural or artificial carboxylic acids have been studied from a variety of viewpoints. Silyl carboxylic acids, as analogues of carboxylic acids, are highly attractive due to their unique physical and chemical properties as well as their potential reactivity. The applications of silyl carboxylic acids in the carbonyl coupling reactions, silyl radical reactions and esterification are summarized.