Development of catalytic asymmetric reactions based on a molecular assembly

基于分子组装的催化不对称反应的发展

基本信息

批准号：
14572001
负责人：
TAKEMOTO Yoshiji
金额：
$ 2.5万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

项目摘要

1.With an aim of proper alignment of the prepared ammonium catalysts in a micelle, we designed and synthesized four ammonium catalysts, which possess alkyl and poly-ether side-chains into the cinchonidine. Although we have developed a convenient method for the introduction of alkyl and poly-ether groups into the cinchonidine-derived quatemary ammonium salts, the asymmetric alkylation of imino glycinate using these catalysts only gave rise to the corresponding products with lower enantioselectivity than that of the original catalyst.2.We have developed the first enantioselective Ir-catalyzed allylic substitutions of diphenylimino glycinate by using chiral bidentate ligand (up to 98% ee), and also succeeded in the diastereoselective asymmetric synthesis of both diastereomers by simply switching the base employed such as KOH (method A) and LiHMDS (method B).3.Since we succeeded in the enantioselective synthesis of the branch products, we next investigated the asymmetric synthesis of quaternary amino acids using the Ir-catalyzed allylic alkylation of various alaninates. The adoption of method B to phosphate and alaninate gave chiral quaternary amino acids with acceptable yield and stereoselectivity.4.We found that thiourea dramatically enhanced the nucleophilic addition of TMSCN and ketene silyl acetals to nitrones and aldehydes. Furthermore, thiourea bearing a tertiary amino group worked well as a bifunctional organocatalyst, and promoted the Michael reaction of malonates to various nitroolefins with high enantioselectivities. The reaction was also successful without solvent.

1.我们的目的是在胶束中正确排列制备的铵催化剂，我们设计和合成了四个将烷基和聚纤维侧链含有烷基和聚纤维链链催化剂。尽管我们已经开发了一种方便的方法来用于将烷基和聚醚基团引入辛克诺定衍生的准铵盐中，但使用这些催化剂的伊米诺甘氨酸的不对称烷基化仅引起了与原始催化剂的相应产品相应的鉴赏性。通过使用手性二齿配体（最多98％EE）甘氨酸，并且还通过简单地切换所采用的基础（方法A）和LiHMDS（方法B）（方法B）来成功地对两个非对映异构体的非对象选择性不对称合成。酸使用各种烷氨酸的IR催化的烯丙基烷基化。方法B对磷酸盐和丙氨酸的采用给出了可接受的产量和立体选择性的手性季氨基酸。4。我们发现硫脲急剧增强了TMSCN和酮烯丙基尖替氏乙二醇的亲核添加到氮和醛中。此外，带有三级氨基群的硫脲作为双功能有机催化剂效果很好，并促进了丙二酸酯对具有高对映射的各种硝基苯甲酸酯的迈克尔反应。反应也没有溶剂成功。