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Development of Asymmetric Reactions Catalyzed by Chiral Bronsted Acid

手性布朗斯台德酸催化不对称反应的研究进展

基本信息

批准号：
17550046
负责人：
AKIYAMA Takahiko
金额：
$ 2.3万
依托单位：
Gakushuin University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550046/
关键词：
Asymmetric Synthesis Chiral Bronsted Acid Asymmetric Catalyst Imine Cyclization reaction Nitrogen Containing Compound 触媒付加環化反応リン酸 aza Diels-Alder反応ヒドロホスホニル化反応 Mannich型反応 TADDOL BINOL

项目摘要

We already developed and synthesized a chiral phosphoric acid diester starting from (R)-BINOL and demonstrated its catalytic activity as a chiral Bronsted acid. In order to extend the chiral Bronsted acid catalysis, we have studied the enantioselective nucleophilic addition and cycloaddition reaction toward imines.Nucleophilic addition of diisopropyl phosphite with aldimine was catalyzed by a phosphoric acid diester bearing 3,5-(CF_3)C_6H_2 groups on 3,3'-position to give a-aminophosphonate with high enantioselectivity.Aza Diels-Alder reaction of electron-rich dienes such as Danishefsky's diene with aldimine proceeded smoothly to give nitrogen-containing 6-membered rings with high to excellent enantioselectivity.The reverse electron-demand aza Diels-Alder reaction of electron-rich alkene with aza Diene also proceeded smoothly to give tetrahydroquinoline derivatives with excellent enantioselectivity by means of a phosphoric acid diester bearing 9-anthryl group on the 3,3'-positions.We have found that the phosphoric acid diesters, derived from (R)-BINOL, exhibit excellent catalytic activity as chiral Bransted acid for the nucleophilic reactions and cycloaddition reactions to give nitrogen-containing compounds with good to excellent optical purity.

我们已经开发和合成了一种手性磷酸二酯从（R）-BINOL和证明其作为手性布朗斯台德酸的催化活性。为了拓展手性Bronsted酸催化作用，我们研究了亚胺的不对称亲核加成和环加成反应，在3，5-（CF_3）C_6H_2上带有3，5-（CF_3）C_6H_2基团的磷酸二酯催化下，亚磷酸二异丙酯与醛亚胺的亲核加成反应，3 ′-位上的电子转移反应，得到了对映选择性较高的α-氨基膦酸酯。富二烯如Danishefsky的二烯与醛亚胺的反应可以顺利地进行，得到具有高至优异的对映选择性的含氮六元环。富烯烃与氮杂二烯的反应也顺利进行，通过含9-羟基的磷酸双酯，得到了具有优良对映选择性的四氢喹啉衍生物。我们已经发现，衍生自（R）-BINOL的磷酸二酯作为手性布朗斯台德酸对亲核反应和环加成反应显示出优异的催化活性，从而得到具有良好至优异光学纯度的含氮化合物。