Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (8): 2574-2581.DOI: 10.6023/cjoc202203019 Previous Articles     Next Articles



岑守义, 张志鹏*()   

  1. 华东理工大学化学与分子工程学院 上海 200237
  • 收稿日期:2022-03-08 修回日期:2022-04-11 发布日期:2022-04-22
  • 通讯作者: 张志鹏
  • 基金资助:
    国家自然科学基金(21702059); 上海市浦江人才计划(18PJ1402200)

Synthesis of Biphenanthrol-Based Confined Chiral Phosphoric Acid

Shouyi Cen, Zhipeng Zhang()   

  1. School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai 200237
  • Received:2022-03-08 Revised:2022-04-11 Published:2022-04-22
  • Contact: Zhipeng Zhang
  • Supported by:
    National Natural Science Foundation of China(21702059); Shanghai Pujiang Program(18PJ1402200)

Chiral phosphoric acids derived from 1,1'-binaphthyl-2,2'-diol (BINOL) and 1,1'-spirobiindane-7,7'-diol (SPINOL) have been widely applied in asymmetric catalysis and displayed excellent enantioselectivities in hundreds of reactions. However, in catalytic asymmetric reactions that involve less sterically hindered nonaromatic substrates, these Brønsted acids usually provide unsatisfactory enantioselectivities due to the relatively loose chiral environment around the catalytically active site induced by the inherent orientational property of the 3,3'-substituents which extend outwardly. In order to develop chiral phosphoric acids that are compatible with these substrates, 9,9'-biphenanthryl-10,10'-diol (BIFOL)-based confined phosphoric acid was designed by introducing two aromatic substituents which extend inwardly onto the 1,1'-positions of BIFOL. By employing cheap and commercially available m-dibromobenzene as starting material, the key intermediate 8-bromophenanthren- 9-ol which undergoes oxidative coupling to afford 1,1'-dibromo-9,9'-biphenanthryl-10,10'-diol was first synthesized. After introducing two aryl substituents through Suzuki-Miyaura coupling, the obtained aryl-substituted BIFOL was converted to the targeted molecule by reacting with phosphoryl chloride and hydrolyzing. The structure of the obtained phosphoric acid was confirmed by single crystal X-ray diffraction analysis.

Key words: chiral phosphoric acid, compact chiral environment, biphenanthrol, 9,9'-biphenanthryl-10,10'-diol, 8-bromo- phenanthren-9-ol, organocatalyst, 9,9'-biphenanthryl-10,10'-diol (BIFOL)