不对称催化是现代有机合成与催化科学的核心研究领域,手性配体的设计创新是推动领域突破的关键。螺环骨架凭借优异的刚性结构与手性诱导能力,成为优势手性配体平台。近年来,以硅原子为手性中心的硅螺环骨架,凭借更大原子半径、更长C-Si键、独特电子效应与空间构型,成为手性配体设计的新兴方向。本文系统梳理手性硅螺环骨架的发展历程,重点阐述SPSiOL、SPOSiOL两类核心硅螺环骨架的构建方法,总结双膦、双亚磷酸酯、双噁唑啉、膦-噁唑啉等硅螺环配体的结构特征与设计思路;全面综述其在铑、镍、钯、铜、铱催化的不对称氢化、氢硅化、氢硼化、环异构化、[2+2+2]环加成、烯烃炔基胺化等反应中的应用进展。本文旨在为新型手性硅螺环配体的理性设计、催化机制研究及不对称合成应用提供系统参考,推动手性硅化学在医药、材料等领域的发展。
Asymmetric catalysis stands as a core domain in modern organic synthesis and catalysis science, wherein the design and innovation of chiral ligands represent the decisive driving force for breakthroughs. Benefiting from their rigid structures and outstanding chiral induction capability, spirocyclic scaffolds have become privileged platforms for chiral ligand development. In recent years, silicon-stereogenic spirocyclic frameworks have emerged as a new frontier in chiral ligand design, owing to the larger atomic radius, longer C-Si bonds, unique electronic effects, and distinct spatial configurations of silicon. This review systematically summarizes the developmental history of chiral silicon-centered spirocyclic scaffolds, with a focus on the synthetic strategies for two privileged cores, SPSiOL and SPOSiOL. The structural features and design philosophies of diverse silicon-spiro ligands, including diphosphines, bisphosphites, bisoxazolines, and phosphine-oxazolines, are comprehensively discussed. Their applications in Rh-, Ni-, Pd-, Cu-, and Ir-catalyzed asymmetric hydrogenation, hydrosilylation, hydroboration, cycloisomerization, [2+2+2] cycloaddition, and intramolecular alkynylamination are thoroughly overviewed. This review aims to provide a systematic reference for the rational design of novel chiral silicon-spiro ligands, mechanistic investigations, and synthetic applications, thereby promoting the advancement of chiral silicon chemistry in pharmaceuticals and materials.
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