Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (10): 1017-1029.DOI: 10.6023/A20070335 Previous Articles     Next Articles

Special Issue: 纪念南开大学化学学科创建100周年



程磊, 周其林   

  1. 南开大学化学学院元素有机化学研究所 天津 300071
  • 投稿日期:2020-07-29 发布日期:2020-09-16
  • 通讯作者: 周其林
  • 作者简介:程磊,1993年出生于湖北钟祥,2015年在吉林大学获得学士学位,目前在周其林教授指导下攻读博士学位.研究兴趣是镍催化烯烃参与的不对称碳碳成键反应;周其林,南开大学化学学院教授.1982年在兰州大学化学系获得学士学位,1987年在中科院上海有机化学研究所获得博士学位,导师黄耀曾研究员.1988年至1996年先后在华东理工大学、德国Max-Planck研究所、瑞士Basel大学和美国Trinity大学做博士后研究.1996年加入华东理工大学,任副教授、教授,1999年受聘教育部"长江学者"计划特聘教授,任南开大学元素有机化学研究所教授.2009年被增选为中国科学院院士.主要研究领域为金属有机化学、有机合成方法学、不对称催化等.
  • 基金资助:

Advances on Nickel-Catalyzed C(sp3)-C(sp3) Bond Formation

Cheng Lei, Zhou Qilin   

  1. Institute of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
  • Received:2020-07-29 Published:2020-09-16
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21790332, 21790330).

Transition metal-catalyzed coupling reactions are powerful synthetic methods for the C-C bond formation. Many coupling reactions such as Heck reaction, Negishi coupling, and Suzuki coupling have been widely applied in the syntheses of pharmaceuticals, functional materials and fine chemicals. In those coupling reactions, a C(sp2)-C(sp2) bond is formed in high efficiency and selectivity. However, in contrast to the C(sp2)-C(sp2) couplings, the C(sp3)-C(sp3) couplings are more difficult and develop late. Because the C(sp3)-C(sp3) bonds are ubiquitous in organic compound, the C(sp3)-C(sp3) bond formation is the central task of research in organic chemistry. In the past two decades, a great effort has been devoted to the development of cross-coupling reactions between alkyls to construct C(sp3)-C(sp3) bonds and impressive progress has been achieved. Among the transition metal catalysts that have been used in the construction of C(sp3)-C(sp3) bonds, nickel was found to be a preferable one, exhibiting unique activity and selectivity. Nickel catalysts promote the activation of alkyl electrophiles via radical catalytic cycles and inhibit and/or manipulate β-H elimination reactions. Nickel has several variable valence states and can flexibly participate in tandem reactions and reductive cross-coupling reactions. All these characteristic natures contribute to the success of nickel catalysts in the construction of C(sp3)-C(sp3) bonds. In this review, we will describe the advances on the nickel-catalyzed C(sp3)-C(sp3) bond-forming reactions. The main contents of this review include:the cross-coupling of alkyl electrophiles with organometallic reagents; the coupling involving a C(sp3)-H bond activation in the presence of directing group; the coupling co-catalyzed by nickel and photocatalyst; the reductive coupling of two alkyl electrophiles; and the additions of nucleophiles or electrophiles to alkenes such as hydroalkylation and difunctionalization of alkenes. The review will focus on the latest developments of nickel-catalyzed alkyl coupling reactions in the past two decades. The mechanisms of each reaction are discussed in detail for understanding the reactions.

Key words: nickel catalysis, C(sp3)-C(sp3) bond formation, cross-coupling, addition reactions of olefins, asymmetric synthesis