An efficient asymmetric hydrophosphonylation of unsaturated amides catalyzed by rare-earth metal amides [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) with phenoxy-functionalized chiral prolinols

作者：Fei, Zenghui; Zeng, Chao; Lu, Chengrong; Zhao, Bei^*; Yao, Yingming^*

来源：RSC Advances, 2017, 7(31): 19306-19311.

DOI：10.1039/c7ra00468k

• PHOSPHA-MICHAEL ADDITION
• ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS
• RING-OPENING POLYMERIZATION
• ENANTIOSELECTIVE HYDROPHOSPHONYLATION
• AMINO PHOSPHONATES
• CONJUGATE ADDITION
• COMPLEXES BEARING
• DIETHYL PHOSPHITE
• N-ACYLPYRROLES
• ALDEHYDES

An asymmetric hydrophosphonylation reaction of diethyl phosphite with alpha, beta-unsaturated amides catalyzed by [(Me3Si) 2N](3)RE(mu-Cl) Li(THF)(3) (RE = Sc (1), Y (2), La (3), Yb (4) and Lu (5)) with H2Ln ((S)-2,4-R-2-6-[[2-(hydroxydiphenylmethyl) pyrrolidin-1-yl] methyl] phenol) (R = Bu-t (H2L1); R = 1-cumyl (H2L2) and R = 1-adm (H2L3)) was disclosed. The effects of different central metals and proligands on the addition reaction were tested and it was found that the combination of Sc complex 1 and ligand H2L2 gave the best results. An excellent chemical yield (up to 99%) and good to high enantioselectivities (varied from 73 to 89%) were achieved with a relatively broad scope of the unsaturated amides. The active species in the current system was also discussed.

• 出版日期2017
• 单位苏州大学