Citation: Xiangning Chen, Han Zhou, Hanmin Huang. Diastereo- and enantioselective conjugate addition of α-keto esters to nitroalkenes: Complete switch in the enantioselectivity by tuning the metal center or rigidity of the ligand[J]. Chinese Journal of Catalysis, ;2015, 36(1): 57-67. doi: 10.1016/S1872-2067(14)60199-6 shu

Diastereo- and enantioselective conjugate addition of α-keto esters to nitroalkenes: Complete switch in the enantioselectivity by tuning the metal center or rigidity of the ligand

1.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China

Corresponding author: Hanmin Huang,
Received Date: 15 May 2014
Available Online: 15 June 2014
Fund Project: 国家自然科学基金(21222203, 21172226和21133011). (21222203, 21172226和21133011)

A series of efficient catalytic systems has been developed to control the dual enantioselectivity of the conjugate addition of α-keto esters to nitroalkenes. The use of the chiral diamine (1S,1'S)-1,1'-biisoindoline as a chiral ligand with either (Cu(OAc)₂·H₂O or Ni(OAc)₂·4H₂O as the catalyst provide facile access to the respective enantiomers resulting from the conjugate addition reaction with high levels of enantioselectivity (94% ee vs 93% ee). Furthermore, the use of Cu(OAc)₂·H₂O as the metal center allowed the enantioselectivity of the conjugate addition reaction to be switched through the tuning of the rigidity of the chiral diamine ligand (94% ee vs 94% ee).
- Chiral diamine,
- Conjugate addition,
- Dual enantioselectivity,
- Metal center,
- Rigid ligand
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