Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (10): 1919-1940.DOI: 10.6023/cjoc201406030 Previous Articles     Next Articles

Reviews

发展高效的不对称Suzuki-Miyaura偶联反应及其合成应用

徐广庆, 赵庆, 汤文军   

  1. 中国科学院上海有机化学研究所 生命有机化学国家重点实验室 上海 200032
  • 收稿日期:2014-06-19 修回日期:2014-07-22 发布日期:2014-08-11
  • 通讯作者: 汤文军 E-mail:tangwenjun@sioc.ac.cn
  • 基金资助:

    国家自然科学基金(No. NSFC-21272254)、上海浦江人才计划(No. STCSM-13PJ1410900)、中组部青年千人计划资助项目.

Development of Efficient Asymmetric Suzuki-Miyaura Cross-Coupling and Applications in Synthesis

Xu Guangqing, Zhao Qing, Tang Wenjun   

  1. State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai 200032
  • Received:2014-06-19 Revised:2014-07-22 Published:2014-08-11
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21272254), the Science and Technology Commission of Shanghai Municipality (No. 13PJ1410900), and the “Thousand Plan” Youth Program.

A series of structurally rigid, sterically bulky biaryl monophosphorus ligands were designed and synthesized to investigate the reactivity and stereoselectivity of asymmetric Suzuki-Miyaura cross-coupling reaction. High efficiencies were achieved in sterically demanding cross-couplings for the synthesis of tetra-ortho-substituted biaryls with various functionalities. Sterically demanding aryl-alkyl Suzuki-Miyaura couplings between di-ortho-substituted aryl halides and secondary alkylboronic acids were also successful. In achieving efficient asymmetric Suzuki-Miyaura coupling, we implemented a new concept by employment of a chiral biaryl monophosphorus ligand developed in the group as well as utilization of a secondary interaction between two coupling partner. Using a π-π interaction of a benzooxazolidinone substituent with one aryl partner, we developed enantioselective biaryl couplings containing ortho-carbonyl substituents. High enantioselectivities were also achieved in biaryl coupling containing ortho-oxy substituents by utilizing a polar-π interaction between a polar bis(2-oxo-3-oxazolidinyl)phosphonic (BOP) substituent and one aryl partner. The methodology enabled us for the first time to implement efficient asymmetric Suzuki-Miyaura coupling in total synthesis and accomplish the syntheses of chiral biaryl natural products korupensamines A and B, ultimately a concise and stereoselective synthesis of michellamine B.

Key words: monophosphorus ligand, sterically demanding, Suzuki-Miyaura coupling, secondary interaction, total synthesis