丰产金属催化烯烃的脱氢硅基化反应
Earth-Abundant Metal-Catalyzed Dehydrogenative Silylation of Alkenes
DOI: 10.12677/jocr.2026.143032, PDF,   
作者: 郭 杰*：山东孚日新能源材料有限公司，山东 潍坊；苏启轩, 刘鑫俊, 吴江涛, 郑士博, 王佳钰, 刘 畅：金华职业技术大学制药工程学院，浙江 金华
关键词: 丰产金属；脱氢硅基化；烯基硅烷；Earth-Abundant Metals； Dehydrogenative Silylation； Vinylsilanes
摘要: 烯基硅烷和烯丙基硅烷是合成化学与材料科学中一类重要的有机硅中间体。相较于传统的亲核取代反应和贵金属催化体系，丰产金属催化的烯烃脱氢硅基化反应以简单硅烷为硅源、烯烃为底物，副产物仅为氢气，具有高原子经济性、良好的官能团耐受性和环境友好等优势。本文系统综述了铁、钴、镍、铜、锰等丰产金属催化烯烃脱氢硅基化反应的研究进展。首先，对比了脱氢硅基化与硅氢化、silyl-Heck反应在催化循环层面的本质差异。随后，分金属类别详细介绍了各催化体系的底物适用范围、硅烷类型、化学选择性及局限性。文章还总结了各金属催化体系的共同机理特征：金属–硅中间体的生成、烯烃插入及β-氢消除。最后，展望了该领域未来的发展方向，包括无过渡金属的光/电催化策略、不对称脱氢硅基化构建硅手性中心，以及理论计算(尤其是DFT)在催化剂理性设计中的应用前景。本综述为开发高效、绿色、高选择性的脱氢硅基化反应提供了系统性参考。
Abstract: Alkenyl silanes and allyl silanes represent a crucial class of organosilicon intermediates in synthetic chemistry and materials science. Compared to traditional nucleophilic substitution reactions and noble metal-catalyzed systems, metal-catalyzed olefin dehydrosilination offers significant advantages: it employs simple silanes as silicon sources, uses olefins as substrates, produces only hydrogen as a byproduct, exhibits high atomic economy, excellent functional group tolerance, and environmental friendliness. This review systematically examines research progress on metal-catalyzed olefin dehydrosilination using iron, cobalt, nickel, copper, manganese, and other abundant metals. First, it compares the fundamental differences between dehydrosilination, hydrosilylation, and silyl-Heck reactions at the catalytic cycle level. Subsequently, it details the substrate scope, silane types, chemical selectivity, and limitations of each catalytic system by metal category. The article also summarizes common mechanistic features across systems—including formation of metal-silicon intermediates, olefin insertion, and β-hydrogen elimination. Finally, it outlines future directions including transition-metal-free photo-/electrocatalytic strategies, asymmetric dehydrosilination for constructing chiral silicon centers, and the application potential of theoretical calculations (particularly DFT) in rational catalyst design. This review provides a comprehensive framework for developing efficient, green, and highly selective dehydrosilination reactions.
文章引用：郭杰, 苏启轩, 刘鑫俊, 吴江涛, 郑士博, 王佳钰, 刘畅. 丰产金属催化烯烃的脱氢硅基化反应[J]. 有机化学研究, 2026, 14(3): 363-377. https://doi.org/10.12677/jocr.2026.143032

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