Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (12): 2912-2919.DOI: 10.6023/cjoc201604022 Previous Articles     Next Articles



邢爱萍a, 田密a,b, 王来来a   

  1. a 中国科学院兰州化学物理研究所 羰基合成与选择氧化国家重点实验室 兰州 730000;
    b 中国科学院大学 北京 100039
  • 收稿日期:2016-04-11 修回日期:2016-06-29 发布日期:2016-08-22
  • 通讯作者: 王来来
  • 基金资助:

    国家自然科学基金(Nos. 20773147,21073211,21174155)资助项目.

Novel Chiral C3-Symmetric Monophosphite Ligands: Synthsis and Catalytic Performance in Asymmetric Hydroformylation and 1,4-Conjugate Addition

Xing Aipinga, Tian Mia,b, Wang Lailaia   

  1. a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000;
    b Graduate University of Chinese Academy of Sciences, Beijing, 100039
  • Received:2016-04-11 Revised:2016-06-29 Published:2016-08-22
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 20773147, 21073211, 21174155).

A family of the novel chiral helical C3-symmetric monophosphite ligands has been synthesized from axially chiral (R)-or (S)-H8-BINOL and PCl3. The performance of these ligands in asymmetric catalysis was evaluated by the Rh-catalyzed asymmetric hydroformylation of styrene, and the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to acyclic enones. The catalytic hydroformylation of styrene gave rather high conversion (93%), high regioselectivity (b/n=95/5) and low enantioselectivity[28% ee (R)] using ligand (R)-2 in tetrahydrofuran at room temperature. Under the optimal 1,4-conjugate addition of ZnEt2 to chalcone 3a conditions, eleven acyclic enones 4a~4k were all converted smoothly to the 1,4-adducts with high enantiomeric excess. Using Cu(OTf)2 as catalyst precursor and Et2O as solvent at -20℃, the structure of ligand (R)-3 comprising a partially hydrogenated 2,2'-(1,1'-binaphthyl)-phosphite scaffold and an adamantyl moiety was key factor in improving catalytic activity and the enantioselectivity with up to 98% yield and 72% ee (R). The sense of enantiodiscrimination of the reaction was controlled by the configuration of the diaryl phosphite moieties.

Key words: asymmetric hydroformylation and 1,4-conjugate addition, monophosphite, the Rh- and Cu-complexes, styrene and acyclic enones, catalytic activity and enantioselectivity