有机化学    

综述与进展

卡宾插入硅氢键的研究进展

陈绍维a,b, 刘珊珊*b,*, 沈晓*b,c,d,*   

  1. a磷矿及其共伴生资源绿色高效开发利用全国重点实验室 化工与制药学院 武汉工程大学 武汉 430072;
    b复杂生命体代谢与调控全国重点实验室 高等研究院 有机硅化合物与材料教育部工程研究中心 武汉大学 武汉 430072;
    c元素有机化学全国重点实验室 南开大学 天津 300071;
    d武汉大学深圳研究院 深圳 518057
  • 收稿日期:2026-07-06 修回日期:2026-08-21
  • 基金资助:
    国家重点研发计划(2022YFA1506100); 国家自然科学基金委(22471201, 22531010, 22501209); 元素有机化学全国重点实验室开放基金 (2026PT0001); 深圳市科技计划(JCYJ20230807090212023; JCYJ20250604122531001)资助项目.

Recent Advances in Carbene Insertion into Si-H Bonds

Shaowei Chena,b, Shanshan Liub,*, Xiao Shenb,c,d,*   

  1. aState Key Laboratory of Green and Efficient Development of Phosphorus Resources, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei 430072;
    bState Key Laboratory of Metabolism and Regulation in Complex Organisms, The Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Wuhan University, Wuhan, Hubei 430072;
    cState Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071;
    dShenzhen Research Institute of Wuhan University, Wuhan University, Shenzhen, Guangdong 518057
  • Received:2026-07-06 Revised:2026-08-21
  • Contact: *E-mail: ssliu2018@whu.edu.cn; xiaoshen@whu.edu.cn
  • Supported by:
    Project supported by the National Key R&D Program of China (2022YFA1506100), the National Natural Science Foundation of China (22471201, 22531010, 22501209) and the Shenzhen Science and Technology Program (JCYJ20230807090212023 and JCYJ20250604122531001).

有机硅化合物在功能材料、有机合成和药物化学中不可或缺,这促使化学家持续追求高效、高选择性的C-Si键构建方法。在现有策略中,卡宾插入 Si-H键因具有原子经济性、温和的反应条件以及可高效构建结构多样的有机硅烷而脱颖而出。本综述基于四种反应类型,对该领域的最新进展进行了系统的评述:过渡金属催化转化(着重于2020年以来的进展)、生物催化反应、光诱导转化以及热生成自由卡宾与Fischer卡宾的插入反应。对于每一类反应,本文审视了卡宾前体、催化机理、底物范围及立体控制性能。通过探讨这些不同途径的独特优势与内在局限,本综述描绘了卡宾Si-H插入化学当前的研究前沿与尚未解决的关键挑战。

关键词: 有机硅, 卡宾, 硅氢键, 碳硅键, 过渡金属催化, 生物催化, 光化学反应

Organosilicon compounds are indispensable across functional materials, organic synthesis, and medicinal chemistry, driving chemists to pursue efficient and highly selective methods for C-Si bond construction. Among existing strategies, carbene insertion into Si-H bonds stands out by virtue of its atom economy, mild reaction conditions, and efficient access to structurally diverse organosilanes. This Review systematically summarizes the latest advances in this field across four reaction categories: transition-metal-catalyzed transformations (with emphasis on progress since 2020), biocatalytic reactions, photo-induced conversions, and the insertion of thermally generated free carbenes and Fischer carbenes. For each category, the carbene precursors, catalytic mechanisms, substrate scope, and stereocontrol performance are examined. By discussing the distinctive advantages and inherent limitations of these divergent pathways, this Review delineates the current research frontier and the unresolved key challenges in carbene Si-H insertion chemistry.

Key words: Organosilicon, Carbene, Si-H bond, C-Si bond, transition-metal catalysis, Biocatalysis, Photochemical Reactions