有机化学 ›› 2022, Vol. 42 ›› Issue (10): 3295-3301.DOI: 10.6023/cjoc202206041 上一篇    下一篇

所属专题: 不对称催化专辑

综述与进展

金属卡宾参与的对映选择性去对称化反应研究进展

滕明瑜a,*(), 韩涛a, 黄恩和b, 叶龙武a,b,c,*()   

  1. a 云南师范大学化学化工学院 昆明 650500
    b 厦门大学化学化工学院 厦门 361005
    c 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032
  • 收稿日期:2022-06-21 修回日期:2022-07-04 发布日期:2022-11-02
  • 通讯作者: 滕明瑜, 叶龙武
  • 作者简介:
    †贡献相同.
  • 基金资助:
    国家自然科学基金(92056104)

Research Progress on Enantioselective Desymmetrization Reactions Involving Metal Carbenes

Ming-Yu Tenga(), Tao Hana, En-He Huangb, Long-Wu Yea,b,c()   

  1. a College of Chemistry and Chemical Engineering, Yunan Normal University, Kunming 650500
    b College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
    c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2022-06-21 Revised:2022-07-04 Published:2022-11-02
  • Contact: Ming-Yu Teng, Long-Wu Ye
  • About author:
    † These authors contributed equally to this work.
  • Supported by:
    National Natural Science Foundation of China(92056104)

金属卡宾在有机合成中具有非常重要的应用, 其不同的活性可以发生形式多样的化学反应. 以金属卡宾的反应类型分类, 介绍了金属卡宾参与的去对称化C—H插入反应、Buchner反应、Si—H插入反应和B—H插入反应. 在手性铑、钌、铜等催化剂的催化下, 反应可高对映选择性地合成手性碳环化合物、杂环化合物、有机硅化合物和有机硼化合物, 极大地丰富了不对称合成化学的发展.

关键词: 重氮化合物, 金属卡宾, 去对称化, 不对称合成

Metal carbenes have been widely applied in organic synthesis, and they can undergo a variety of chemical transformations due to their versatile reactivities. In this review, the desymmetrization of C—H insertion reaction, Buchner reaction, Si—H insertion reaction and B—H insertion reaction involving metal carbenes is introduced according to the different reaction types of metal carbenes. Under the catalysis of chiral rhodium, ruthenium and copper catalysts, chiral carbocycles, heterocycles, organosilicons and organoborons can be obtained with high enantioselectivity, which greatly enriches the development of asymmetric synthetic chemistry.

Key words: diazo compounds, metal carbene, desymmetrization, aymmetric synthesis