Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (11): 1522-1540.DOI: 10.6023/A23070336 Previous Articles     Next Articles

Special Issue: 庆祝《化学学报》创刊90周年合辑

Perspective

钯(II)催化不对称C(sp3)—H键官能团化研究进展

韩叶强a, 史炳锋a,b,*()   

  1. a 浙江大学化学系 杭州 310027
    b 郑州大学化学学院绿色催化中心 郑州 450000
  • 投稿日期:2023-07-13 发布日期:2023-09-11
  • 作者简介:

    韩叶强, 2016年毕业于浙江工业大学获学士学位, 之后在浙江大学史炳锋教授的指导下攻读博士学位并在2021年获得理学博士学位, 2021年7月加入黄飞鹤教授课题组从事博士后研究. 主要研究方向为不对称碳氢键活化和新型大环体系的高效构筑.

    史炳锋, 博士, 教授, 独立课题组组长. 2001年本科毕业于南开大学化学系, 2006年博士毕业于中科院上海有机所. 2006年到2007年在University of California, San Diego从事博士后研究, 2007年到2010年加入The Scripps Research Institute从事博士后研究. 2010年4月加入浙江大学化学系, 任独立课题组组长, 博士生导师, 主要研究领域为过渡金属催化的惰性键活化及其在天然产物全合成中的应用.

    庆祝《化学学报》创刊90周年.
  • 基金资助:
    国家重点研发计划(2022YFA1504302); 国家自然科学基金(U22A20388)

Palladium(II)-Catalyzed Enantioselective Functionalization of C(sp3)—H Bonds

Yeqiang Hana, Bingfeng Shia,b()   

  1. a Department of Chemistry, Zhejiang University, Hangzhou 310027
    b Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450000
  • Received:2023-07-13 Published:2023-09-11
  • Contact: *E-mail: bfshi@zju.edu.cn; Tel.: 0086-571-88981229
  • About author:
    Dedicated to the 90th anniversary of Acta Chimica Sinica.
  • Supported by:
    National Key Research and Development Program of China(2022YFA1504302); National Natural Science Foundation of China(U22A20388)

Chiral molecules are ubiquitous in nature and play an important role in natural products, pharmaceuticals, agriculture, advanced materials, as well as living organisms. Therefore, the development of efficient strategies to enable the facile construction of enantiopure chiral compounds in an atom- and step-economical manner is of great importance. The enantioselective functionalization of C—H bonds without multi-steps transformation is arguably one of the most powerful and straightforward strategies to fulfill this goal. This emerging research field has been rapidly developed with the innovation of various chiral catalysts and/or ligands in recent years. In particular, significant advances have been achieved in palladium-catalyzed enantioselective functionalization of C(sp3)—H bonds, streamlining the efficient and concise construction of chiral molecules from readily available hydrocarbon feedstocks. The stereoselective functionalization of C(sp3)—H bonds with the assistance of chiral ligand to form a chiral palladacycle intermediate, which could be transformed into various chemical bonds to form functionalized chiral compounds, has attracted tremendous attention. Thus, this perspective summarizes the advances on palladium(II)-catalyzed enantioselective functionalization of C(sp3)—H bonds via asymmetric C—H palladation. According to the type of C—H bonds, this perspective is classified into several sections, including methyl C(sp3)—H bonds, methylene C(sp3)—H bonds in constrained cycloalkanes, functionalization of methylene C(sp3)—H bonds adjacent to α-heteroatom, benzylic methylene C(sp3)—H bonds, and unbiased methylene C(sp3)—H bonds. The emphasis of this perspective focuses on the discussion of the philosophy of developing novel chiral ligands and the mode of stereocontrol. The remaining limitations and challenges regarding to chemo- and enantioselective control in this field is also discussed. Further development of new chiral ligands and catalytic systems is expected to address these issues and expands the scope of this powerful synthetic strategy. We anticipate that this perspective might inspire more efforts to this emerging research field and the strategy might find wide applications in the synthesis of complicated chiral molecules, such as natural products and drugs.

Key words: palladium, enantioselectivity, C—H activation, palladacycle intermediates, chiral ligand