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

合成了1，1 ′-（2，2 ′-二氨基）联萘的酰胺衍生物，并考察了它们作为手性配体的不对称合成能力。在叔胺存在下，1，1 ′-（2，2 ′-双苯甲酰氨基）联萘（BINAMIDE）与Yb（OTf）_3形成配合物。该配合物催化巴豆酰亚胺与环戊四胺的不对称Diels-Alder反应，具有很高的对映体选择性（endo/exo=>95：5，> 95% e.e.）。苯环上的取代基影响催化剂的活性和选择性。同时发现Yb（OTf）_3的干燥度对获得活性催化剂是重要的。本文报道了抗生素-肉霉素的催化不对称甲醛全合成。合成的关键步骤是BINAMIDE配合物催化溴代丙烯酰亚胺和环戊二烯的不对称Diels-Alder反应，活性催化剂的结构目前尚不清楚。合成了BINAMIDE的环状衍生物，其中两个酰基通过闭环复分解（RCM）连接。研究了Yb（OTf）_3-TMSCl刚性催化剂的晶化和X射线衍射分析，并发现Yb（OTf）_3-TMSCl催化对甲苯磺酰亚胺和甲基苯乙烯的亚胺烯反应生成高烯丙基胺。

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.