The Application Of The Aziridino Alcohol Chiral Ligands In Asymmetric Henry And Reformatsky Reaction

This paper studies the application of the aziridino alcohol chiral ligands in catalytic asymmetric Henry reaction and catalytic asymmetric Reformatsky response.1. The application of chiral aziridino alcohol ligands with two stereogenic centers in the catalytic asymmetric Henry.Based on the research in our laboratory, this chapter chiefly re-expands the application of the chiral aziridino alcohol ligand L* with two chiral centers. The catalytic efficiency and asymmetric induction of L* and its diastereoisomer were studied in the catalytic asymmetric Henry reaction. The two diastereoisomers had different induced effects, but the L*(S, R) had better stereo-selectivity. Also, the effects of temperature, solvent and additive to this reaction were investigated. Finally, we found that in the presence of DiMPEG (10% mol) the reaction of benzaldehyde with nitromethane could afford the corresponding product in up to 58.7% yield and in up to 67.1% cnantiomeric excess at-50℃in 24 h. And we expanded the substrates, got the yields among 32.2-71.6% and ee values among 33.4-63.9%.2. The application of chiral trityl aziridino alcohol ligand in the catalytic asymmetric Reformatsky.This chapter studies the application of the chiral ligand L* in the asymmetric Reformatsky reaction. In this paper, we tested three aziridino alcohol ligands and found chiral trityl aziridino alcohol ligand L* had the best effect. Considering the experiment data and cost, we employed 25% mol L* for the reaction. With alkyl zinc as zinc source, we found that the experiment data of ZnMe2 were better than that of ZnEt2 both in the yield and ee value. When we used THF:Et2O=2:3 as solvent and PhP3P=S (30% mol) as additive, the yields of benzaldehyde and ethyl bromide were greatly improved. And the reaction reached 61.4% of the ee value and 62.7% of the chemical yield at the best condition.