Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (9): 2168-2174.DOI: 10.6023/cjoc201603004 Previous Articles     Next Articles



刘倩倩, 洪玉标, 郑煜, 薛明强   

  1. 苏州大学材料与化学化工学部 苏州 215123
  • 收稿日期:2016-03-03 修回日期:2016-04-27 发布日期:2016-05-06
  • 通讯作者: 薛明强
  • 基金资助:


Bis(β-diketiminato) Lanthanide(Ⅱ) Complexes-Catalyzed Hydro-phosphonylation of Aldehydes/Ketones and Diethyl Phosphite

Liu Qianqian, Hong Yubiao, Zheng Yu, Xue Mingqiang   

  1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123
  • Received:2016-03-03 Revised:2016-04-27 Published:2016-05-06
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No.21372171).

The hydrophosphonylation of aldehydes/ketones was explored by use of seven bis(β-diketiminato) lanthanide(Ⅱ) complexes[Eu(L2,6-ipr2)2·CH3C6H5, L2,6-ipr2=[N(2,6-iPr2C6H3)C(Me)]2CH- (1); Eu(L2,6-Me2)2(THF), L2,6-Me2=[N(2,6-Me2C6H3)C(Me)]2CH- (2); Eu(L2,4,6-Me3)2(THF), L2,4,6-Me3=[N(2,4,6-Me3C6H2)C(Me)]2CH- (3); Eu(L2,6-ipr2Ph)2, L2,6-ipr2Ph=[(2,6-iPr2C6H3)NC(Me)CHC(Me)N(C6H5)]-(4); Sm(L2,6-ipr2)2·CH3C6H5 (5); Yb(L2,6-ipr2Ph)2 (6); Yb(L2-Me)2(THF), L2-Me=[N(2-MeC6H4)C(Me)]2CH- (7)] as the catalysts. All complexes were found to be able to catalyze the hydrophosphonylation between aromatic or heterecycle aldehyde and diethyl phosphite with high activity under wild conditions. All the reactions gave the products in 90%~99% yields using 0.08 mol% of complex 7 at 25℃ under solvent-free. The catalyst activity was found to depend on the β-diketiminato ligands with the sequence of L2,6-Me22,4,6-Me32,6-ipr2≈L2,6-ipr2Ph. This catalyst system showed a wide scope of aldehydes. Besides, bis(β-diketiminato) lanthanide(Ⅱ) complexes could also efficiently catalyze the hy-drophosphonylation of unactive ketones with diethyl phosphite and showed a good substrate scope.

Key words: β-diketiminato, lanthanide(Ⅱ) complexes, hydrophosphonylation, aldehydes/ketones