有机化学 ›› 2020, Vol. 40 ›› Issue (2): 255-275.DOI: 10.6023/cjoc201910009 上一篇    下一篇

综述与进展

过渡金属催化的有机硼试剂对醛酮的不对称加成研究进展

祝东星a, 徐明华a,b   

  1. a 中国科学院上海药物研究所 新药研究国家重点实验室 上海 201203;
    b 南方科技大学化学系 深圳格拉布斯研究院 广东深圳 518055
  • 收稿日期:2019-10-10 修回日期:2019-10-27 出版日期:2020-02-25 发布日期:2019-11-07
  • 通讯作者: 徐明华 E-mail:xumh@sustech.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.21672229,81521005,21971103)、国家科技重大专项(No.2018ZX09711002-006)资助项目.

Transition Metal-Catalyzed Asymmetric Addition of Organoboron Reagents to Aldehydes and Ketones

Zhu Dong-Xinga, Xu Ming-Huaa,b   

  1. a State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203;
    b Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055
  • Received:2019-10-10 Revised:2019-10-27 Online:2020-02-25 Published:2019-11-07
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21672229, 81521005, 21971103) and the National Science & Technology Major Project of China (No. 2018ZX09711002-006).

手性芳基醇是一类重要的合成砌块,广泛存在于许多生物活性分子以及天然产物中,因此,高效高选择性地构建该类化合物是有机化学家们一直关注的研究热点.金属试剂对羰基化合物的不对称加成是构建手性芳基醇的一个简单高效的方法,其中,有机硼试剂由于其方便易得、稳定、低毒、官能团耐受性好等优点而被广泛用于醛、酮的不对称加成反应中.本文综述了过去二十年来过渡金属催化的有机硼试剂对醛、酮的不对称加成反应研究进展,并介绍了一些方法在生物活性手性分子合成中的应用.

关键词: 不对称合成, 手性醇, 有机硼试剂, 过渡金属催化, 不对称加成

Chiral aryl alcohols are prevalent in a broad range of biologically active compounds, pharmaceutical agents and natural products. They also constitute a broad class of optically active building blocks for the synthesis of important chiral compounds. In recent years, organoboron reagents are widely used in organic synthesis as they possess advantages of ready availability, low toxicity, good air and moisture stability as well as high functional group compatibility. Since the first report of rhodium-catalyzed asymmetric addition of aryl boronic acids to aryl aldehydes in 1998 by Miyaura, the use of organoboron reagents in asymmetric addition to various carbonyl compounds under various transition-metal catalyses has been intensively investigated. Over the past two decades, transition metal-catalyzed asymmetric addition of organoboron reagents to aldehydes and ketones has proved as one of the most direct and powerful methods for accessing versatile optically active alcohols. The development and progress of a wide range of chiral ligands for Rh, Ru, Pd, Ir, Cu, Ni and Co catalysis for asymmetric addition of organoboron reagents to aldehydes and ketones are summarized, and the achievements in enantioselective synthesis of chiral aryl alcohols and their applications in the synthesis of related biocative products are described. Among them, rhodium and ruthenium-catalyzed enantioselective additions have received considerable attention. In the cases of activated carbonyl compounds such as α-aryl ketoesters and α-diaryl diketones, excellent results can be attained in terms of both yield and enantioselectivity. However, it remains a daunting challenge for highly enantioselective addition to simple unactivated aldehydes and ketones owing to the difficulty in overcoming stereo differentiation. Future efforts in the community would focus on developing new effective transition-metal catalysts in addressing these issues by promoting efficient transformation and controlling excellent enantioselectivity.

Key words: asymmetric synthesis, chiral alcohols, organoboron reagents, transition-metal catalysis, asymmetric addition