Citation: Liu Qianqian, Hong Yubiao, Zheng Yu, Xue Mingqiang. Bis(β-diketiminato) Lanthanide(Ⅱ) Complexes-Catalyzed Hydro-phosphonylation of Aldehydes/Ketones and Diethyl Phosphite[J]. Chinese Journal of Organic Chemistry, ;2016, 36(9): 2168-2174. doi: 10.6023/cjoc201603004 shu

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

1.
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123

Corresponding author: Xue Mingqiang, xuemingqiang@suda.edu.cn
Received Date: 3 March 2016
Revised Date: 27 April 2016

Fund Project: the National Natural Science Foundation of China 21372171

Figures(2)

The hydrophosphonylation of aldehydes/ketones was explored by use of seven bis(β-diketiminato) lanthanide(Ⅱ) complexes[Eu(L^{2, 6-ipr2})₂·CH₃C₆H₅, L^{2, 6-ipr2}=[N(2, 6-ⁱPr₂C₆H₃)C(Me)]₂CH^- (1); Eu(L^{2, 6-Me2})₂(THF), L^{2, 6-Me2}=[N(2, 6-Me₂C₆H₃)C(Me)]₂CH^- (2); Eu(L^{2, 4, 6-Me3})₂(THF), L^{2, 4, 6-Me3}=[N(2, 4, 6-Me₃C₆H₂)C(Me)]₂CH^- (3); Eu(L_Ph^{2, 6-ipr2})₂, L_Ph^{2, 6-ipr2}=[(2, 6-ⁱPr₂C₆H₃)NC(Me)CHC(Me)N(C₆H₅)]^-(4); Sm(L^{2, 6-ipr2})₂·CH₃C₆H₅ (5); Yb(L_Ph^{2, 6-ipr2})₂ (6); Yb(L^2-Me)₂(THF), L^2-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 L^{2, 6-Me2} < L^{2, 4, 6-Me3} < L^{2, 6-ipr2}≈L_Ph^{2, 6-ipr2}. 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.
- β-diketiminato,
- lanthanide(Ⅱ) complexes,
- hydrophosphonylation,
- aldehydes/ketones
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