Synthesis of New Axially Chiral Ligand Library and Application to Asymmetric Synthesis of Biologically Active Compounds.

点击翻译按钮获取中文摘要

Amide derivatives of 1,1'- (2, 2'-bisamino) binaphthalene were prepared and examined their ability as a chiral ligand for asymmetric synthesis. 1, 1'- (2, 2'-Bisbenzoylamino) binaphthalene (BINAMIDE) complexed with Yb(OTf)_3 in the presence of tertiary amine. The complex catalyzed asymmetric Diels-Alder reaction between crotonyl imide and cyclopentadine with high diastereo-and enantioselectivity (endo/exo=>95 : 5, >95% e.e.). A substituent on the phenyl ring influenced the activity and selectivity. We also found that dryness of Yb(OTf)_3 is important to obtain active catalyst. Catalytic asymmetric formal total synthesis of antibiotics, sarkomycin was accomplished. A key step of the synthesis was catalytic asymmetric Diels-Alder reaction of bromoacryimide and cyclopentadiene using BINAMIDE complex.The structure of the active catalyst is not clear now. Cyclic derivatives of BINAMIDE were prepared, in which two acyl groups were connected by ring closing metathesis (RCM). Crystallization and X-ray analysis of the rigid catalyst is under investigation.We also found that Yb(OTf)_3-TMSCl catalyze imino ene reaction of tosylimine and methylstylene to give homoallyl amines.