第27期Chinese Journal of Chemistry论坛•硅化学

Solid polymer electrolytes (SPEs), especially those based on poly(ethylene oxide) (PEO), have garnered significant attention in the field of all-solid-state lithium batteries due to their high processability and low cost, advantages that are typically hard to achieve with their inorganic counterparts. However, the poor ionic conductivities have retarded their further applications in all-solid-state lithium batteries. Herein, we report a series of corona-shaped two-dimensional polyaramid (2DPA) derivatives that improve the overall performance of PEO-based SPE, including ionic conductivity, ion transference number, and electrochemical stability. We demonstrate that the unique corona topology, consisting of a rigid two-dimensional polyaramid core and flexible poly(ethylene glycol) (PEG) chains grafted at its periphery, effectively inhibits the crystallization of the PEO matrix, thus enhancing the ionic conductivity. Furthermore, the 2D polyaramide core provides enriched Lewis acidic binding sites for counter anions, suppressing the anion motion and resulting in selective lithium ion transport. The assembled all-solid-state batteries exhibit improved cycle performance and higher stability. Such a heterostructural polymer design strategy showcases the promising potential of novel 2D polymer derivatives in ion transport optimization in SPEs.

The strong Si-F bond was easily to activate by DBU catalytic system.Various disiloxanes bearing tolerated functional groups were successfully synthesized in moderate to excellent yields from fluorosilanes and hydrosilanes.H,O as the oxygen donor was found in this catalytic system.

尽管醇衍生物与氯硅烷的偶联反应已经报道，但醇与氯硅烷的脱氧硅基化反应研究很少，本研究工作发展了一种铬催化策略，实现了醇、醚、羰基化合物的脱氧官能团化反应

The Importance of Silacycles: Silicon as a Carbon Isostere in bioactive molecules and functional materials. Ø Challenges: Structural diversity of silacycles is limited by synthetic methods. Two Strategic Pathways: Expansion with Allenoates – Access to exocyclic enoate-substituted silacyclohexenes. Ø Expansion with Alkynes – Access to axially chiral silacyclohexenyl arenes.

有机硅烷在现代药物化学与复杂分子合成领域具有重要价值。特别是，硅原子独特的原子半径与电负性差异可显著调控候选药物分子的亲脂性、膜渗透性等生理活性。过渡金属催化烷基碳中心构筑通常依赖配位导向基团或π共轭体系实现区域与对映选择性控制。然而，硅基团缺乏共轭电子效应与定向配位能力，在不对称碳-碳偶联反应中难以作为有效的辅助基团发挥作用，导致该类反应极具挑战性。 研究团队开发了钴催化含硅、锗烯烃的不对称氢烷基化新策略。通过配体结构定向修饰，实现了对立体化学决定步骤——烯烃氢金属化步骤的选择性精准控制，建立了非共轭硅基团诱导的高区域选择性和高对映选择性控制新模式。该项研究不仅为功能有机硅烷合成提供了新技术支撑，更为无配位和共轭基团底物的不对称偶联反应开发提供了重要案例。

Silacycles have attracted increasing attention because they have a multitude of applications ranging from organic synthesis, medicinal chemistry to materials science. Within this context, considerable efforts have been devoted to the development of synthetic methods for silacycles. Among them, transition-metal-catalyzed construction of C−Si bonds to access silacycles has emerged as the most popular and direct means. Typical strategies include: (1) annulation of silicon-based frameworks; (2) ring expansion of strained three- or four-membered silacycles; and (3) annulation of silicon reagents with organic molecules via forming two C−Si bonds. In contrast to tremendous progress achieved in the first two strategies, the development of the third strategy, although intriguing, lags far behind due to the scarcity of silicon reagent types and their diverse reactivity. The existing reports are mainly focused on transition-metal-catalyzed cycloaddition of organosilicon reagents with unsaturated compounds via a silylene transfer strategy. Therefore, developing new reaction modes for the synthesis of silacycles by using new silicon reagents and substrates is highly desirable.

In conclusion, we developed the nickel-catalyzed enantioselective hydrosilylation of nalkyl-substituted gem-diflu or oalkenes,which enables the generation of chirala-difluoromethylsilanes with excellent regio- and enantioselectivity. Moreover, the simultan e ousconstruction of carbon- and silicon-stereogenic centers was achieved with excellent diastereo- and enantioselectivity using prochiral silanes.

Enzymatic stereoselectivity has typically been unrivalled by most chemical catalysts, especially in the conversion of small substrates. According to the “lock-and-key theory”,1 enzymes feature confined active sites to accommodate their specific reacting substrates, a feature that is typically absent in chemical catalysts. An interesting case in this regard is the formation of cyanohydrins from ketones and HCN, as this reaction can be catalyzed by various classes of catalysts, including biological, inorganic, and organic ones.2 Here we report the development of broadly applicable confined organocatalysts3 for the highly enantioselective cyanosilylation of ketones, including the challenging 2-butanone (steric effects were described as A-values). The selectivity (98:2 e.r.) obtained toward its pharmaceutically relevant product is unmatched by any other catalyst class, including engineered biocatalysts. Our results suggest that confined chemical catalysts can be designed that are as selective as enzymes in converting small, unbiased substrates, while still providing a broad scope.

Chiral silanols are important synthetic targets and have garnered increasing attention in the materials and pharmaceutical industries over recent decades. A promising approach for their efficient synthesis is asymmetric silane oxidation. While chemists have developed several transition-metal-catalyzed systems for asymmetric hydrolytic oxidation of silanes, no biocatalytic methods have been available for enantioselective synthesis of Si-stereogenic compounds, including chiral silanols.

含硅手性中心的有机硅化合物在合成化学、医药化学及材料科学中具有重要应用价值。然而，与碳手性中心相比，硅手性中心的高效构建方法仍然较为有限。通过对具有相同取代基的前手性硅烷进行去对称化反应，是构建硅手性中心的有效策略之一。近年来，过渡金属催化及布朗斯特酸催化的去对称化反应在手性有机硅化合物的合成中取得了一定进展。相比之下，路易斯碱催化在该领域的研究仍相对不足。本研究工作发展了几种基于路易斯碱催化的前手性硅烷去对称化策略，高效合成了一系列结构多样的含硅手性中心的有机硅化合物。

有机硅化合物凭借其独特的结构和性质，在合成化学、材料化学及药物化学等领域展现出广阔的应用价值与研究前景。因此，开发高效、模块化合成 高附加值有机硅化合物的新策略，兼具重要的科学意义与极高的应用价值。近年来，过渡金属催化烯烃或炔烃与硅基试剂的硅基化反应已经成为合成 有机硅化合物的有效手段。其中，有机硅锌试剂的Si−Zn键的离子性相对更弱，而共价性更强，使其在保持较好反应活性的同时还具有良好的官能团 兼容性。然而，传统卤化物硅锌试剂反应体系存在对空气中的水氧敏感性高，反应需要严格的无水无氧操作以及反应集中于两组分的碳硅交叉偶联的 局限。因此，开发新型具有良好稳定性及反应性的有机硅试剂作为新型硅基化合成子应用于有机硅化合物的合成是具有挑战且迫切需要解决的课题。本课题组通过阴离子配位调控策略，设计、制备了一类对空气和水具有良好稳定性、使用方便的固体特戊酸硅锌试剂，有效解决了传统卤化物硅锌试剂存在的对水氧高度敏感、易分解、保存困难以及反应活性可控性差等关键问题，并成功将其应用于镍催化烯烃的碳硅化、配体调控的镍催化内炔烃 区域发散式硅氢化反应，以及C–O键活化硅基化，合成了多官能团取代的烷基和烯基硅烷。此外，将该新型硅锌试剂拓展至钴催化不饱和烃的硅酰胺 化反应，实现了硅代（脱氢）多肽高效、模块化合成，为含硅（脱氢）多肽的合成提供了一条全新的合成途径，也为含硅药物的开发提供了新的思路。

Herein, we report the invention of a novel carbene precursor, α-trifluoromethyl diazosilanes reagent and its application in the synthesis of (difluoromethylene)cyclopropanes and chiral trifluoromethyl epoxides. The gram scale reaction and down-stream transformation based on the removable silyl group demonstrated the synthetic potential of the reaction.

The radical-mediated dearomatization of aromatic systems to generate cyclohexadienyl intermediates represents a crucial strategy for constructing three-dimensional molecular architectures. Conventional approaches typically through ipso-addition and subsequent proton/oxygen/carbon dioxide trapping to suppress rapid re-aromatization, significantly constraining product diversity. Furthermore, dearomative bifunctionalization reactions—which offer enhanced step- and atom-economy—remain substantially underdeveloped. Herein, we disclose a copper-catalyzed radical dearomative 1,4- and 1,2-carbosilylation strategy applicable to diverse unactivated (hetero)aromatic substrates to selectively construct spiro- or fused-cyclic products. The resulting vinyl and allylic silanes serve as versatile synthetic handles for downstream transformations, enabling the rapid construction of sp³-rich polycyclic scaffolds that are highly valuable in drug discovery. Mechanistic and DFT studies indicate that the reaction commences with copper(I)-silicon-mediated halogen atom transfer of readily available aryl iodides to generate aryl radicals. These reactive species exhibit dual pathways: direct ipso-addition to aromatic rings or 1,5-hydrogen atom transfer followed by alkyl radical-mediated ortho-addition. Subsequent trapping of the resulting dienyl radicals by copper(II)-silicon species yields complex polycyclic systems containing cyclohexadienylsilicon frameworks with excellent chemo-, regio- and diastereoselectivity. This methodology not only establishes a novel paradigm for copper-catalyzed radical dearomative bifunctionalization but also provides an efficient radical ipso- and ortho-addition platform for synthesizing architecturally intricate polycyclic compounds.

硅和锗是重要的半导体材料，组分调控和表面改性可以有效调节其理化性质，在电子和通讯等领域有着广阔的应用前景。然而，硅和锗相关化学键的共价特性使得常规用来调节离子型半导体的合成和表面化学方法无法直接用于此类材料。我们课题组从硅和锗特殊的共价键/离子键共存的成键形式出发，先后发现了几类新的硅和锗的偶联和加成反应模式，用于实现晶体硅的常温常压合成和无催化剂参与的硅表面芳基化，开发了金属掺杂硅和锗纳米晶的固体反应，从而有效调控硅锗半导体材料的光学和电学性质，也拓展了对硅和锗成键方式及其对相关材料性质影响的知识边界。

以弱配位抗衡阴离子稳定的硅正离子为核心的催化策略，已成为高效构建结构多样化有机硅化合物的关键手段。该策略的核心作用机制为：硅正离子参与反应消耗后外源的取代硅烷在亲电试剂的协同作用下通过亲核性基团的脱除实现硅正离子的循环再生。然而，反应体系中存在的溶剂、芳环、不饱和键、杂原子等多种亲核体，易与取代硅烷中的亲核性基团发生亲核竞争，进而引发反应活性与选择性难以调控、立体选择性难以实现等问题。鉴于硅正离子催化过程普遍涉及碳正离子中间体，通过外源(手性)电子供体对反应所涉碳正离子的亲核性进行精准调控，有望从热力学、动力学及稳定性等多维度实现其反应活性的调控，不仅可发展新型合成方法、实现反应的优异(立体)选择性，更能为结构多样化含硅有机分子的构筑方法开发提供重要支撑。

The duality of trialkyl(aryl)silanes render them valuable and versatile synthons. To date, a number of strategies have been developed to enable aryl transfer from even simple and inert trialkyl(aryl)silanes. However, exploration of alkyl reactivity in general manifold remains challenging. Herein, we report that a mild photoredox catalysis effects exclusive C(sp3)–Si bond alkylation of chemically innocuous trialkyl(aryl)silanes. By resembling beta-silicon hyperconjugation effect with catalytically generated proximal arene radical cation, we leverage the high stability of silyl cation to drive selective C(sp3)–Si bond cleavage, thus unlocking a new strategic concept in prolific use of quaternary organosilane library. Experimental and computational mechanistic studies confirm the attenuation of C–Si bond with proximal radical cation, revealing positive charge accumulation at silicon during transition state.

Organosilicon/organogermane compounds have received increased attention over the past decades because of their unique properties and broad applications in pharmaceuticals, materials and organic synthesis. As a result, developing C-Si/Ge bond formation reactions that incorporate silicon/germane atoms into organic molecules is not only a prerequisite but also a driving force to unlock the full potential of organosilanes/organogermanes. Among current strategies, transition-metal catalyzed silylative/germylative difunctionalization of olefins with silyl/germanyl organometallic reagents has emerged as one of most powerful protocols. However, high reactivity and hard to availability of those metallic reagents largely diminish their further application. By contrast, reductive silylative/germylative difunctionalization of alkene under transition-metal catalysis utilizing easily accessible chlorosilanes/chlorogermanes would be much more fascinating, but still unexplored. Herein, we present a set of examples of reductive difunctionalization of alkenes, including silylative/germylative alkylation of activated olefins with alkylbromides and chlorosilanes or chlorogermanes, silylative alkylation of acrylonitrile with NHPI esters and chlorosilanes, as well as silylative alkylation of acrylonitrile with α-functionalized alkylbromides and chlorosilanes under nickel catalysis. The main feature of these protocols is easily accessibility of substrates, good functional group tolerance and high structure diversity of products.

Organosilanes are a class of versatile compounds and have already been utilized as synthetic linchpins, catalysts, adhesion promoters, sensors, etc. in both fundamental research and industrial processes. Here, we report a highly efficient rhodium-catalyzed enantioselective hydrosilylation of unactivated alkenes, achieving excellent regioselectivity and high enantioselectivity. The use of a commercially available chiral ferrocene-based phosphine-oxazoline ligand was crucial in achieving excellent chiral induction and high reactivity with undirected unactiviated alkenes, delivering Si-stereogenic monohydrosilanes in high yields and excellent enantioselectivities. This protocol represents a robust, scalable method for the enantioselective synthesis of Si-stereogenic monohydrosilanes, featuring a low catalyst loading, a broad substrate scope and exceptional functional group and heterocycle tolerance. Moreover, the late-stage functionalization of complex motifs opens a new avenue for incorporating chiral silicon motifs into pharmaceuticals and bioactive compounds.

硅橡胶在热防护涂层中应用广泛，但存在两大关键失效模式：在极高温环境下易发生链断裂与氧化，在极低温度条件下则因结晶化导致粉化，这些因素共同限制了其在宽温域应用中的服役寿命（工作温度范围一般为–55 °C至300 °C）。为突破这一局限，我们提出一种集成“主链刚性、主链柔性与侧链柔性”的聚合物设计策略，合成了一类新型室温固化苯撑基聚硅氧烷，相关涂层在经历–196 °C至1150 °C后展现出优异的隔热与抗烧蚀性能。

有机硅化合物是有机合成领域最重要的合成中间体之一，近年来有机硅化合物在医药、农药、材料等领域也展现出巨大的潜力。因此，发展高效、新颖的有机硅化合物的合成新策略已成为当前有机合成最活跃的领域之一。近年来，我们在有机硅化学领域实现了：1）利用去对称化策略，实现了双烯基硅烷的硼化/质子化反应，高效实现了含硼手性硅分子的构建；2）发展了亚甲基环丙烷类化合物的连续氢硅化反应，实现了多立体中心手性硅杂环戊烷的高效构建。

In recent years, redox reactions have harnessed light or mechanical energy to enable the formation of chemical bonds. We postulated a complementary approach that electromagnetic induction could promote the redox reaction of organic molecules using a rotating magnetic field and metal rods. Here, we report that magnetoredox radical fluoroalkylation and cross-electrophile coupling reactions using rotating magnetic field and metal rods. Such a magnetoredox approach introduces new reaction design parameters such as magnetic intensity, rod size, and rotating frequency, enabling highly selective formation of chemical bonds through multifaceted regulation, which could potentially represent an attractive and powerful strategy for the divergent synthesis of organic molecules.

稀土-氢、元素键的稳定策略 稀土-氢、元素键反应性的精准调控

Nitrogen-containing silanes represent a large class of organosilicon compounds that have found wide applications in contemporary synthetic chemistry,organometallic chemistry, coordination chemistry, and functional materialsowing to their distinct structural properties. Herein, we report a visible-light-induced radical-radical coupling of polysubstituted silanes with NHPI esters toachieve Si-N bond formation. This reaction produces a wide range of silazanesin good yields. Mechanistic studies suggest the involvement of silyl andnitrogen-centered radicals. This strategy provides a practical and generalapproach for constructing structurally diverse silazanes, which is potentiallyvaluable for the development of functional materials.

利用硅杂四元环固有环张力，对其进行催化活化并使之开环，是合成有机硅的有效策略之一。然而传统方法大多涉及到昂贵有毒过渡金属催化剂的使用，不利于其在药物合成中的应用1-2。有鉴于此，本研究以六氟异丙醇为溶剂，结合硅原子上取代基的优化，首次实现了可见光催化含硅四元环的活化开环及其与缺电性烯烃的自由基加成，并结合进一步水解，合成了取代多样性季硅醇（图1）3。研究表明，六氟异丙醇与硅原子配位，以及硅原子上富电性芳基（邻甲氧基苯基）的引入，是硅杂四元环得以发生可见光催化氧化开环的关键（图2） 。反应可通过流动化学有效放大，新策略亦可拓展至与炔基碘等其它自由基受体的反应；所得季硅醇在中心硅原子上保留羟基活性位点，具有可进一步参与亲核取代转化，生成更多类型季硅结构的潜力，为扩展含硅化学空间提供了新颖实用的反应工具（图3）。

Catalytic syntheses of silaoxycarbocyclics from an interrupted Catellani reaction of 3-iodochromones with bridged olefins and octamethyl-1,4-dioxacyclohexasilane is described. This protocol involves the oxidative addition of chromonyl-norbornyl-palladacycle generated through successive oxidative addition of Pd(0) to 3-iodochromones, migratory insertion of NBE and intramolecular ortho-C(sp2)−H activation to the tetrasilane, thus motivating a (4 + 6) annulation and ring expansion. The synthetic practicality is further proved by the late-stage modification of pharmaceuticals and natural products. Additionally, a chromone-thiocoumarin transmutation enabled by Lawesson’s reagent was achieved.

Organosilicon compounds have found wide applications in material sciencesandinbiorelatedstudies.1 The introduction of silicon atoms into carbocycles can greatly affect their properties. This carbon-to-silicon switch can often greatly enhance the lipophilicity while lowering the toxicity of the product. However, strategic and precise introduction of a silicon atom into a chiral cyclic product represents a long standing challenge, which is related to the high tendency of silicon atoms to form hypervalent species that are prone to transmetalation or desilylation. The challenge in synthesis of organosilicon compounds and the versatile reactivity of C−Si bonds as a synthetic handle have aroused increasing attention.2 The increasing demand for silacycles in diverse scaffold calls for development of efficient and new synthetic methods starting from readily available reagents, especially with excellent chiral induction. We developed an alternative strategy of “remote” [2σ+2σ] annulation between SCBs and an unsaturated coupling partner that affords a seven-membered ring.

过渡金属催化的不对称分子间氢硅化反应构建相邻立体中心，在合成中仍面临挑战。本文报道了一种由手性亚磷酸酯配位的铑配合物，能够催化β,β-双取代烯酰胺的氢硅化反应，从而以高度区域选择性、非对映选择性和对映选择性的方式，合成具有两个立体中心的重要α-氨基硅烷类化合物。通过调控底物的几何构型与配体的手性构型，可实现立体发散性合成所有可能的立体异构体。

To overcome limitations of Cu-based catalysts in the Rochow–Müller reaction, we synthesized XIn–CeCuO catalysts designed to form p-n heterojunctions between In2O3 and CeCuO. TEM confirmed p-n heterojunction formation at their interfaces. Studies revealed this interaction increased copper electron density, promoted active intermediate production, and significantly enhanced silicon conversion. Systematic evaluation showed the optimized 2In–CeCuO catalyst achieved superior activity (86.7% M2 selectivity and 51.7% Si conversion) far exceeding pristine CeCuO.

While bifunctional allylation reagents have proven effective for constructing complex molecules bearing multiple central chirality,1 their potential for assembling axially chiral scaffolds remains undeveloped. With our ongoing research in enantioselective allylation as well as the asymmetric construction of axial chirality, 2 we developed a BINOL-catalyzed enantioselective allylation of prochiral carbonyl compounds using a type I bifunctional allylation reagent, which affords enantioenriched β-hydroxy silanes. The central chirality of these adducts is then efficiently transferred to axially chiral alkylidenecyclohexanes via an acid/base-controlled, enantiodivergent Peterson elimination. Moreover, this strategy is successfully extended to the enantioselective assembly of axially chiral diaryl ethers with three contiguous chiral elements. Density functional theory (DFT) calculations were performed to elucidate the origin of the enantioselectivity.

While the past few decades have witnessed great advances of the enantioselective synthesis of biaryl atropisomers, the catalytically enantioselective synthesis of atropisomeric acyclic 1,3-dienes is still elusive.1 Building on our ongoing research in transition-metal hydride-catalyzed asymmetric synthesis and the enantioselective construction of axially chiral compounds,2 we developed a platinum-catalyzed enantioselective hydrosilylation of enynes. With a monophosphine ligand L* used, the atropisomeric 1,3-dienes are constructed with good yield and enantioseletivity in excellent regioselectivity. Control experiments show that the steric hinderance amide is essential for the enantioselectivity. Density functional theory (DFT) calculations are conducted to elucidate the origin of the enantioselectivity. Crucially, the basic additive such as KOH and K3PO4 works as a proton shuttle to promote this reaction.

The direct cleavage of the C(Ar)–NO₂ bond is challenging but the most straightforward method to convert unactivated nitroarenes into high-value-added derivatives both in industry and academia. However, thermally driven denitrative transformations are hampered by a narrow substrate scope or reliance on expensive catalysts, driving the development of alternative activation paradigms. Herein, we report a photocatalyst-mediated redox-neutral radical substitution strategy for aromatic denitrative C(sp²)-C(sp³) bond formation via photoredox-catalyzed dual activation of unactivated nitroarenes and silyl enol ethers, which are activated simultaneously to realize the α-arylation of various ketones. This transformation requires only a catalytic organic photosensitizer, exhibits broad functional group tolerance—including various heterocycles—and affords products amenable to diversification for the modification of natural products and ligands. Furthermore, the olefin scope is successfully extended to α-substituted styrenes

光催化不对称合成具有绿色、高效和可持续性等优势，且能突破传统热催化反应能垒，在温和条件下实现挑战性的转化，是合成复杂手性药物分子和功能材料的强大工具。有机硅试剂价廉易得，种类繁多，稳定性强，无毒，且氧化电势低，是光催化反应中一类常用的自由基前体。然而，由于自由基中间体活性高，寿命短，导致背景反应强、立体选择性调控极具挑战性。针对这一问题，我们发展了手性Lewis酸辅助光催化和光催化剂/手性Lewis酸协同催化两种策略，高效高选择性实现了几类热催化下难以发生的不对称转化，为组胺拮抗剂、托品酸及其衍生物等高附加值手性分子的合成提供了简单、高效途径。

Synthesis of Organofluorine Compounds with Fluoroalkyl Acylsilanes

The role of CO2 in organic synthesis is generally embodied in two aspects: as C1 feedstock to be incorporated into value-added products or as promoter/catalyst to enhance reaction selectivity without being incorporated. Although both routes have been well established, it is rarely reported yet highly promising to achieve CO2-modulated divergent synthesis along with CO2 fixation in one simultaneous process from the perspective of sustainable and synthetic chemistry. Herein we report a CO2-controlled chemoselective 1,4-hydroxyfunctionalization of silacyclobutanes for the modular access of diverse silanol derivatives with potentially biological activity, which are previously difficult to prepare by other means. The resultant functional group attached to the terminal carbon can be regulated and switched from hydrogen atom to halogens by the presence of CO2 under electrochemical conditions. The CO2 has a dual role as it serves as an inhibitor to keep iodide ion from attacking the electropositive silicon, and is sacrificed via electrochemical reduction into carbonate and carbon on the cathode to fulfill CO2 fixation. Upon this, iodide ion is released and subsequently oxidized into iodine, followed by in situ capture of the electronegative carbon to afford the 1,4-hydroxyhalogenation product. Notably, the synthetic utilization of this protocol is further demonstrated by the straightforward and concise preparation of silicon-containing bioactive precursor in a 68% total yield (Cf. 2% yield in previous report). This method features undivided cell, broad scope and diverse derivatizations, thereby should open up a new scenario of the pivotal role of CO2 in multi-aspects.

The scarcity of synthetic methods to access enantiopure silicon-based tetralin mimics has severely hampered their exploration in medicinal chemistry. Our work provides a direct, catalytic, and asymmetric solution to this long-standing problem, thereby unlocking a new class of potential bioactive compounds for pharmaceutical development. Despite the important contribution of Xu and Song's enantioselective [4+2] annulation of benzosilacyclobutenes with cyclopropenes and alkynes, the formidable challenge of employing allenes remains unaddressed. Such substrates introduce significant complexity, with the potential for more than 8 isomers. Moreover, silicon-containing chiral tetralins with more general substitution patterns and tolerance for diverse functional groups are an underexplored yet highly sought after target. Herein, we have developed a novel chiral perfluorophenyl-substituted phosphoramidite ligand that enables highly chemo-, regio- and enantioselective palladium-catalyzed [4+2] annulation between benzosilacyclobutenes and a wide variety of allenes.

Modular Synthesis of Functionalized Cyclotetrasiloxane (D4) Monomers toward Tailored Polysiloxanes

硅宾是卡宾的硅元素类似物。2025年，我们创制了介离子硅宾，并研究了其配位化学、单硅原子转移、异构化等新颖化学属性。

发展新型有机硅材料，与碳基材料融合乃至替代是有机硅材料未来发展重要方向之一。但是，目前有机硅合成方法较少，限制了有机硅材料的快速发展。近些年，我们发展了Heck反应、巯基-环氧反应、多组分聚合反应、羟基-双键反应等多种合成新方法用于制备有机硅材料，尤其是具有荧光特性的硅氧烷基功能材料。以Heck反应为例，从含乙烯基有机硅单体（包括线型二硅氧烷、环硅氧烷和笼型倍半硅氧烷）出发，与各种卤代芳香单体反应制备了系列硅氧烷基荧光聚合物。该合成方法简单高效，且通过改变硅氧烷单元结构和单体种类能够实现材料荧光性能的调控。并且，发现硅氧烷并非常规认知的共轭阻断连接单元，与单体相比，硅氧烷连接后荧光发射波长发生大的红移，最高红移达200nm以上。通过系列模型化合物合成、性能对比及机理研究，发现硅氧烷可作为共轭连接单元发挥共轭效应，即硅氧烷的超共轭效应；或可激活空间共轭效应，通过调控传统生色团之间的堆积方式，赋予固态和溶液中的双态高效发光。利用其优异的荧光特性，能够作为多功能化学传感器用于检测各种分析物。例如，这些材料可作为高效荧光探针，选择性高效检测硝基苯类爆炸物、金属离子、农药、食品保鲜等；作为潜指纹可视化材料，在日光灯下实现在多种基材上对3级指纹的有效识别，具有高的分辨率和对比度，且材料无毒，有望在刑侦领域得到应用。以上结果证实了Heck反应的高效性，有望发展成为有机硅合成新方法，部分解决有机合成方法少的问题。该方法能够用于设计制备更多新型有机硅功能材料，拓展其应用范围，为实现与碳基材料高效融合乃至替代奠定基础。

The construction of silicon-stereogenic centers via silicon–carbon bond cleavage remains challenging. We design silanes containing a hydroxyl group in the molecule, and adopt a strategy of activating the silicon–carbon bond via the formation of a pentacoordinate silicon intermediate. By using an inexpensive copper catalyst, the silicon–carbon bond is cleaved stereoselectively, thus addressing the challenge of constructing silicon-containing oxygen heterocyclic scaffolds with a silicon-stereogenic center.

An unusual Si–B functional group exchange reactions of hydrosilanes with hydroboranes simply enabled by BH3 as a catalyst is reported. Our methodology works for various aryl, alkyl hydrosilanes and different hydroboranes with the tolerance of general functional groups (up to 115 examples).

As an unusual type of radicals, carbene anion radical exhibits two reactivities of both radical and carbanion on the same carbon atom, presenting unique and intriguing dual radical and carbanion reactivity. Continuing our interest in diazo chemistry, we aimed to develop an iodide-assisted photocatalytic stereo-controlled alkylation of alkenes with diazo compounds. Importantly, iodide plays a crucial role in the alkylation of alkenes rather than cyclopropanation.

In recent years, borate anions have shown valuable applications across various fields, including organic synthesis, materials science, energy storage devices, and biological and pharmaceutical studies. In our research, we developed a series of new borate anions that exhibit intriguing reactivities toward small molecules and unsaturated substrates. Through a reductive B-B coupling of 9-borafluorene, we successfully synthesized the hexaaryl-substituted diboron(6) dianion. Notably, this compound exhibits the unique ability to undergo homolytic B-B bond cleavage at room temperature, resulting in the formation of boryl radical anions. Furthermore, based on a diborencine macrocycle, we successfully trapped a single electron, forming a B-B one-electron σ-bond.

Silicon-stereogenic organosilanes represent a type of novel chemical space that have been increasingly used in the field of organic synthesis, materials, medicinal chemistry and agrochemistry. As a consequence, great effort has been paid to the catalytic enantioselective construction of diverse Si-chiral organosilanes, and an array of elegant approaches based on catalytic asymmetric desymmetrizations of prochiral silanes and (dynamic) kinetic transformations of racemic silanes have been established. Despite significant advances, constructing Si-chirality relies mainly on noble-metal catalyzed desymmetrization, and the potential of asymmetric organocatalysis to construct Si chirality is largely unexplored, although organocatalysis is well established as the third pillar of asymmetric catalysis. Moreover, efficient synthesis of multifunctional Si-stereogenic organosilanes and sp3-rich silacycles that can serve as platform molecules for diversity-oriented synthesis remains very limited.

In recent years, Me3SiCF2H has been developed as a direct difluoromethylation reagent for the synthesis of α-CF2H carbinols using different initiators, such as KF, CsF, t-BuOK etc. However, these initiators are not effective in activating Me₃SiCF₂H to accommodate nucleophilic difluoromethylation of various carbonyl compounds. A major reason for this is the significantly higher bond dissociation energy (BDE) of the Si–CF₂H bond in Me₃SiCF₂H (0.436) compared to that of the Si–CF₃ bond (0.220), which hinders its cleavage by previous initiators.This work reports a novel, moisture-tolerant Ag₂O/TBAI initiation system that enables efficient and direct nucleophilic difluoromethylation of a broad range of carbonyl compounds under ambient air at room temperature. Mechanistic studies indicate that the success of this strategy hinges on the in-situ generation of the true active initiator, TBAOH, via the reaction of Ag₂O/TBAI with trace amounts of water. This methodology has been successfully applied to the synthesis of a bioactive molecule containing 4-(difluoromethyl)-piperidin-4-ol scaffold.

Organosilanes are important building blocks in organic synthesis and find broad applications in materials science and medicinal chemistry. Traditional methods for their synthesis typically involve the reaction of silyl electrophiles with organometallic reagents or the use of silyl nucleophiles with carbon-based electrophiles. Recently, cross-electrophile coupling has emerged as an alternative strategy for constructing C–Si bonds. However, these methods often require stoichiometric amounts of metal reductants such as Mn or Zn, leading to the generation of significant metal salt waste, which limits their practical utility. Building on our previous work in metallaphotoredox-catalyzed, organic-reductant-mediated cross-electrophile coupling, we report herein a photoredox/nickel-catalyzed reductive C–Si coupling of aryl halides with chlorosilanes using silylamine as an organic reductant. This approach eliminates the need for metallic reductants and exhibits broad tolerance for both chlorosilanes and chlorohydrosilanes, offering a complementary and more sustainable route to organosilanes via reductive C–Si bond formation.

Boron-containing compounds are finding valuable applications in catalysis, synthetic chemistry, molecular materials, and drug discovery. The development of powerful and versatile synthetic methods to access complex organoboron compounds is highly desirable and profoundly meaningful. One promising approach involves the rational design of new boron-based catalyst, synthon and reagent. Since 2021, our group has been dedicated to engineering metal-mimetic borenium catalyst, boron-carbon diradical synthon, and borylation reagent for establishing efficient synthetic protocols. These protocols facilitate the convenient construction of a wide range of previously inaccessible or challenging organoboron skeletons, expanding the room of boron chemistry for various applications.

Nitrogen-containing silanes represent a large class of organosilicon compounds that have found wide applications in contemporary synthetic chemistry, organometallic chemistry, coordination chemistry, and functional materials owing to their distinct structural properties. Herein, we report a visible-light induced radical-radical coupling of polysubstituted silanes with NHPI esters to achieve Si−N bond formation. This reaction produces a wide range of silazanes in good yields. Mechanistic studies suggest the involvement of silyl and nitrogen-centered radicals. This strategy provides a practical and general approach for constructing structurally diverse silazanes, which is potentially valuable for the development of functional materials.

Ester and trifluoromethyl groups play crucial roles in chemistry and drug design. However, the implementation of such transformation under wide condition is not an easy work because the C–F bond of trifluoromethyl group possesses high bond energy and extremely difficult to break. Herein, we for the first time present a silylium-ion-initiated method for intermolecular C–F/C–O metathesis, enabling selective activation of inert C(sp3)–F and C(sp3)–O bonds. This approach facilitates the defluoroalkoxylation of trifluoromethyl-substituted substrates and polyfluoroalkanes when combined with ethers or polyethers, thus builds a bridge to convert trifluoromethyl groups into ester/ketone groups along with polyethers upcycling.

The Group 13 or 14 diatomic molecules has garnered significant attention over the past few decades because they not only enhance our understanding of the nature of chemical bonding but also offers promising opportunities for developing new materials with tailored chemical and physical properties. Among these, Si2 and SiGe molecules has intrigued scientists due to their significant role in semiconductor technology. In addition, diborynes (B2), characterized by a boron−boron (B≡B) triple bond represent a unique class that challenges conventional bonding concepts. Despite their fundamental significance, these diatomic clusters are highly unstable, primarily observed in the gas phase through advanced spectroscopic methods. Their instability in condensed phases presents significant challenges for isolation and detailed investigation in laboratory settings. Herein, we report the synthesis, characterization and reactivity exploration of NHSi(N-heterocyclic silylene)-stabilized Si2, SiGe and B2 molecules and highlight their utility in synthetic chemistry.

Dehydrogenative cross-coupling reactions of two less reactive bonds such as two C−H bonds nowadays emerge as a rapidly growing area of research interest and have provided a reliable platform for the construction of C−C bonds from readily available feedstock chemicals. However, the transition metal-catalyzed oxidative coupling of two C−H bonds usually require equivalent oxidants, resulting in the generation of toxic by-products and low atom economy. Recently, we have devised a metal-free photocatalytic system consisting of an organophotocatalyst and a thiol for hydrogen evolution cross-couplings and oxidations. By employing this photocatalytic system, several photocatalytic acceptorless cross-couplings such as Si−H of silanes coupling with O−H of water/alcohols/phenols to form Si−O bonds, as well as with aryl C−H to construct Si−C bonds, aldehydic C−H coupling with O−H of alcohols/phenols to forge esters, and benzylic C−H coupling with aldehydic C−H to afford ketones have been developed, respectively. The corresponding cation intermediates such as silyl cation, acyl cation and benzylic cation, which were generated by an oxidative radical-polar crossover (ORPC) process, were proposed as the key active species to responsible for these cross-couplings. The robustness of this metal-free photocatalytic system was further strengthened by acceptorless oxidation of alcohols to carbonyls, oxidation of benzylic C−H to furnish aldehydes or ketones, and dehalogenative oxidation of benzylic and allylic C−Halo to carbonyls.

Silylcarbamate not only showed the particularity and superiority as an amino protecting group, but also exhibited great potential in specifical transformation such as advanced urea synthesis. However, synthesis of silylcarbamate has received little attention from chemists, though multiple methodologies have been developed to the achieve silylformates and carbamates (urethanes). Two logical approaches to silylcarbamate were the CO2 insertion into Si-N bond of silylamine and transition-metal-catalyzed reduction of CO2 with hydrosilane and amine, which suffered the limitation from high substrate activity and excessive reaction for urea byproduct. Meanwhile, the silanol-isocyanate addition reaction would be envisioned as the potential synthetic route for silylcarbamate. However, very limited reactions were reported with more electrophilic alkyl silanol to show the reactivity and no target products were observed with aryl silanol according to reported results. According to the special transformation of silacarboxylic acid with alkoxide bases, we speculate that exogenous anions generated from nucleophilic addition with silylcarboxylic acids on isocyanate would initiate intramolecular silicon migration for the decarbonylative rearrangement. This advanced strategy exhibited two superiorities: (1) High reactivity of stronger nucleophilic silylcarboxylic acid to isocyanate avoided the invalid reaction of direct silanol-isocyanate addition; (2) Silicon migration for newly formed C-O bond and subsequent decarbonylation rearrangement miraculously ingeniously replaced the role of silylcarboxylic acid to silanol. Thus, herein we reported the first and brand-new example of decarbonylative rearrangement reaction of silylcarboxylic acid.

The activation and transformation of dinitrogen (N2) represents a significant scientific challenge. In particular, while metal nitrides are pivotal intermediates, achieving N–N bond cleavage with 3d metals such as titanium remains scarce. Here we report unprecedented ancillary ligand control over the N2 activation pathway in PCP-ligated titanium complexes upon reduction, wherein aryloxide or diarylamide groups facilitate complete N–N bond scission to dititanium bis(nitride) complexes, whereas the phenyl analogue leads to C–P bond activation of the pincer. Computational studies show that heteroatom-mediated interactions with K+ ions in the secondary coordination sphere promote isomerization of the N2 bridge from end-on to side-on, thereby enabling N–N bond rupture. Moreover, these complexes catalyze the silylation of N2, producing up to 22.0 equiv of N(SiMe3)3, representing the highest TON for Group IV metal systems to date. This ancillary ligand-controlled reactivity highlights a powerful strategy for promoting N2 cleavage at titanium centers and offers new insights into the design of efficient early-metal catalysts for nitrogen fixation.

Polycarbosilanes are unique precursors in the preparation of silicon carbide ceramics and silicon carbide fibers.[1-2] We herein report a cobalt catalyzed hydrosilylation polymerization of dienes and bis-silanes, providing a novel strategy that enabled the efficient synthesis of linear polycarbosilanes. A broad scope of polycarbosilanes was delivered with up to 25 kDa molecular weight, narrow dispersity and decent thermal stability. The further functionalization of polycarbosilanes was accessible while the kinetic process of polymerization was also investigated. Moreover, the introduction of chirality into the polymeric backbone was available, suggesting the application prospects of using polycarbosilanes as chiral organic optoelectronic materials.[3]

A photoinduced alkene vicinal-azidooxime reaction method was developed, in which N-nitrosamines were utilised as bi-functional reagents, with TMSN₃ serving as the azido radical source. The key to this transformation lies in the homolytic cleavage of photosensitive N-nitrosamines, which in turn generates amino radicals and NO radicals. The amino radical then undergoes a nucleophilic substitution reaction with the silicon atom in TMSN₃ to form the key azide radical. This method features a broad substrate scope, requires no additives, and proceeds with high atom economy under mild, room-temperature conditions. Overall, this strategy provides a new route to high-value β-azidooximes, which are im-portant precursors for synthesizing ortho-diamines and other valuable triazole-containing heterocycles.

多肽及蛋白质类药物凭借高亲和力、强特异性和良好安全性，在抗肿瘤、免疫调节等治疗领域展现出广阔应用前景，全球市场持续增长。然而，分子稳定性差、体内半衰期短及清除率高等问题严重制约其临床转化。化学修饰是改善药代动力学性质、提升成药性的关键手段。然而，传统化学修饰策略仍面临反应模式单一、反应条件苛刻、位点选择性差、生物兼容性低等独特挑战。电化学合成以电子为清洁试剂，通过精准调控电极电势，可在温和条件下实现多肽的位点特异性修饰，兼具高选择性、环境友好等优势，为敏感生物大分子的精准改造提供了新的思路。因此，发展面向药学应用、兼具高选择性与良好生物相容性的电化学多肽修饰新策略，对于推动多肽药物创新及临床转化具有重要意义。

Organic silicon compounds are widely used in organic synthesis and pharmaceutical science due to their unique physical and chemical properties. Among them, the efficient catalytic synthesis of silicon-containing heterocyclic compounds with diverse functions has always been a hot research topic in the field of organic silicon chemistry. [1] Considering the value of silacycles in organic synthesis and with the aim of developing new methods for carbon-to-silicon switch strategy, herein, we describe a series of general and highly selective Cu-catalyzed carboboration reactions to provide borylated sila-heterocyclic derivatives.

硅手性化合物在药物化学、新材料开发等多个领域受到广泛关注，因此发展丰产金属催化具有广泛底物普适性的不对称合成硅手性化合物具有重要意义，尤其能够解决硅手性中心中需要特定官能团来实现高立体选择性以及新的硅手性结构。我们利用手性钴络合物催化的不对称硅氢化反应，开发了结构独特的环状硅手性化合物和具有广泛底物范围的线性硅手性化合物的高效高选择性构建的新方法，实现了碳手性中心和硅手性中心同时引入，解决了硅手性中心高立体选择性诱导需要特定大位阻官能团的局限性。

Silacycles are essential structural motifs in silicon-containing functional molecules, which are widely applied in the fields of synthetic chemistry, materials science, and pharmaceuticals. However, the synthesis of silacycles especially medium-sized ones remains a formidable challenge. Herein, we report a general and modular platform technology for the construction of eight-membered benzosilacycles via a Pd-catalyzed three-component cascade reaction involving alkyne insertion, aryl C(sp2)−H activation, and ring expansion. Additionally, we realize the regiodivergent synthesis of eight-membered aryl- and alkenyl-silacycles through a Pd-catalyzed alkenyl C(sp²)−H activation/ring expansion cascade.

To develop efficient visible-light photocatalysts for pollutant degradation, CoZn complexes (CoZn-CP) were used as precursors. Two derivatives, CoZn-CP 400 and CoZn-CP 1000, were prepared by pyrolysis at 400 °C and 1000 °C, then composited in situ with MoSe₂.The structures were characterized by TG, XRD, and SEM. Using RhB, MO, and TC-HCl as model pollutants, the catalytic performance was evaluated by photocurrent, and EIS.This work provides a reference for designing high-performance visible-light photocatalysts with great potential in wastewater treatment.

Lithium–sulfur (Li–S) batteries are considered promising next-generation energy storage systems due to their high theoretical specific capacity (1675 mAh g⁻¹) and energy density (2600 Wh kg⁻¹). However, their practical application is hindered by several key issues, including the polysulfide shuttle effect, poor cycling stability, and safety risks caused by flammable liquid electrolytes. All-solid-state lithium–sulfur batteries (ASSLSBs) offer a potential solution by replacing liquid electrolytes with solid-state electrolytes, which can improve safety and suppress polysulfide migration. Among various solid electrolytes, polyethylene oxide (PEO)-based polymer electrolytes have attracted attention because of their flexibility and good interfacial compatibility. Nevertheless, they suffer from low ionic conductivity and limited ability to inhibit the polysulfide shuttle effect. To address these limitations, composite solid electrolytes incorporating functional fillers have been widely studied. Metal-organic frameworks (MOFs), such as UiO-66, are particularly promising due to their high surface area, tunable pore structure, and strong chemical adsorption capability for polysulfides. However, achieving uniform dispersion of MOFs and constructing efficient ion transport pathways within polymer matrices remain major challenges.

Co-Zr基合金系统被认为是新型永磁材料潜在的候选者，Stroink等人观察到在Co80Zr20条带中加入硼作为稳定剂，可以稳定Co11Zr2亚稳相，而随着电子信息技术和机械智能设备的快速进步，器件的微型化、集成化、高精度化的发展趋势使得永磁薄膜材料的研究变得越来越重要。因此，本研究通过在薄膜中引入B层制备了Si/Ta/Co11Zr2/B/Ta薄膜，通过对退火态合金的微观形貌和磁学性能的研究来探究不同B层厚度及不同退火温度下薄膜的磁性能变化并分析其机理。

Organophotocatalytic Strain-releasing Hydrosilylation of Bicyclo[1.1.0]butanes with Silylboronates

Per-substituted alkenyl fluorides, particularly (E)-isomers that emulate amide bonds, demonstrate significant bioactivity yet present formidable synthetic hurdles. Herein, we introduce a stereoselective carbonyl gem-fluoro(chloro)olefination strategy utilizing a novel sulfoximine reagent to produce (Z)-alkenes, which can subsequently undergo cross-coupling reactions to yield both stereoisomers. Mechanistic studies reveal a predominant 1,5-attack pathway operating under kinetic control. The practical applicability of this method is illustrated through its integration into microfluidic systems, late-stage functionalization processes, and the synthesis of a factor Xa inhibitor as well as an RXR modulator.

A dearomative regio- and diastereoselective 1,2- and 1,4-carbosilylation of diverse unactivated arenes and heteroarenes via a copper-catalyzed radical bifunctionalization strategy that transforms simple aryl iodides into complex, three-dimensional carbosilylated polycycles. We carried out density functional theory (DFT) calculations to study the reaction mechanism of radical generation, radical rearrangement and C─Si coupling processes. The origin of stereoselectivity was further elucidated by structural comparison and independent gradient model (IGM) analysis.