近日，东北师范大学熊涛团队研究了硅-立体硅碳环的催化对映选择性构建。该研究于2026年3月12日发表在《中国化学》杂志上。

硅中心手性硅碳环是一类重要的有机硅化合物，在不对称合成、功能材料和药物化学领域具有广泛应用。

该综述系统总结了催化对映选择性合成方法的最新进展，按催化体系进行分类，并追溯了关键策略的演变——重点关注前手性前体的去对称化，以及动力学拆分和动态动力学不对称转化。该领域最初通过先驱性的钯催化反应建立，特别是张力硅杂环丁烷与炔烃的不对称扩环反应——这是构建环状四有机硅立体中心的基础方法。随后，铑催化体系发展成为高度通用的平台，实现了多种转化，包括：通过脱氢C-H硅基化获得单氢硅烷和杂环化合物；通过分子内氢硅化构建环状单氢硅烷和螺硅二氢茚；以及通过形式[2+2+2]环加成合成二苯并硅咯和螺硅烷。

受经济和可持续性考量驱动，该研究已富有成果地扩展到地球储量丰富的贱金属催化领域：镍催化体系促进了高效的分子内芳基转移和扩环反应，而钴和铜催化的方法则通过连续氢硅化级联反应构建具有连续硅和碳立体中心的硅环。与此同时，无金属有机催化已成为强大的可持续替代方案，手性N-杂环卡宾、手性磷酸、烯胺催化剂和限域型亚氨基二磷酸酯在对映选择性去对称化过程中展现出显著功效。

尽管取得了实质性进展，研究组仍对现有方法提出批判性视角，概述当前存在的挑战与局限，并强调未来研究的有前景方向。当前局限性包括依赖复杂的前手性底物以及长期对贵金属的依赖。未来工作应聚焦于：开发更高效、原子经济的底物合成方法；拓展可持续催化体系，包括贱金属催化、有机催化和生物催化；整合光催化和电催化等新兴技术；以及深化机理理解，以实现对DYKAT等先进策略的理性设计。

附：英文原文

Title: Catalytic Enantioselective Construction of Silicon-Stereogenic Silacarbocycles†

Author: Xiuping Yuan, Kehan Jiao, Jiaqiong Sun, Qian Zhang, Tao Xiong

Issue&Volume: 2026-03-12

Abstract: Comprehensive SummarySilicon-stereogenic silacarbocycles constitute a privileged class of organosilicon compounds with wide-ranging applications in asymmetric synthesis, functional materials, and medicinal chemistry. This review provides a systematic overview of recent advances in catalytic enantioselective synthetic methods, organized by catalytic systems, and traces the evolution of key strategies—with particular emphasis on desymmetrization of prochiral precursors, alongside kinetic resolution (KR) and dynamic kinetic asymmetric transformation (DYKAT). The field was initially established through pioneering Pd-catalyzed transformations, notably the asymmetric ring-expansion of strained silacyclobutanes with alkynes—a fundamental methodology for constructing cyclic tetraorganosilicon stereocenters. Subsequently, Rh-catalyzed systems have emerged as highly versatile platforms, enabling diverse transformations including dehydrogenative C–H silylation for accessing monohydrosilanes and heterocycles, intramolecular hydrosilylation toward cyclic monohydrosilanes and spirosilabiindanes, and formal [2+2+2] cycloadditions for synthesizing dibenzosiloles and silaspiranes. Driven by economic and sustainability considerations, research has fruitfully expanded to encompass earth-abundant base metal catalysis. Ni-catalyzed systems facilitate efficient intramolecular aryl transfer and ring-expansion reactions, while Co- and Cu-catalyzed approaches enable sequential hydrosilylation cascades that construct silacycles bearing consecutive Si and C stereocenters. Concurrently, metal-free organocatalysis has emerged as a powerful sustainable alternative, with chiral N-heterocyclic carbenes (NHCs), chiral phosphoric acids (CPAs), enamine catalysts, and confined imidodiphosphorimidates (IDPi) demonstrating remarkable efficacy in enantioselective desymmetrization processes. Despite substantial progress, we also offer a critical perspective on current methodologies, outline existing challenges and limitations, and highlight promising directions for future research. Current limitations include reliance on elaborate prochiral substrates and historical dependence on precious metals. Future efforts should focus on developing more efficient and atom-economical substrate synthesis, expanding sustainable catalytic systems including base-metal, organo-, and biocatalysis, integrating emerging technologies such as photocatalysis and electrocatalysis, and deepening mechanistic understanding to enable the rational design of advanced strategies such as DYKAT.Key ScientistsIn 2011, Hayashi and Shintani reported a pioneering Pd-catalyzed asymmetric ring expansion of silacyclobutanes with alkynes, enabling the construction of cyclic tetraorganosilicon stereocenters and marking the inception of this field. Subsequently, Takai and coworkers developed a Rh-catalyzed asymmetric synthesis of chiral spirosilabifluorene through sequential Si–H and C–H bond activations. In 2015, Nozaki and Shintani developed an efficient Rh-catalyzed [2+2+2] cycloaddition for the highly enantioselective synthesis of Si-stereogenic dibenzosiloles. In 2018, Xu and colleagues established a Pt-catalyzed tandem hydrosilylation/cyclization, and in 2022, the same group made further breakthroughs in the Rh-catalyzed dynamic kinetic asymmetric hydrosilylation to access Si-stereogenic benzosiloles. Meanwhile, the Song group developed a Rh-catalyzed ring expansion of silacyclobutanes with alkynes, expanding the methodologies for synthesizing axially chiral spirosilanes. In 2021, He et al. made an important contribution through Rh-catalyzed C–H silylation, enabling the enantioselective synthesis of Si-stereogenic monohydrosilanes and various heterocycles. Concurrently, the group of Wang conducted impressive studies on Rh-catalyzed asymmetric hydrosilylation and established a kinetic resolution strategy for the efficient synthesis of Si-stereogenic cyclic monohydrosilanes. More recently, Zhao reported a base-metal-catalyzed intramolecular ring expansion and an Ir-catalyzed enantioselective C–H silylation for constructing Si-stereogenic silacarbocycles, thereby further broadening the catalyst scope in this area. Numerous other researchers have also made important contributions; however, due to space constraints, a comprehensive acknowledgment of all achievements is not feasible within this review.

DOI: 10.1002/cjoc.70499

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70499