Innovation of Asymmetric Cycloaddition Reactions Based on Highly Efficient Stereocontrol in Multinucleating Chiral Reaction Field

多核手性反应领域基于高效立体控制的不对称环加成反应创新

基本信息

批准号：
16550031
负责人：
UKAJI Yutaka
金额：
$ 2.43万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

In order to develop a practical method for the construction of chiral molecules, we have designed a novel chiral system possessing multi-metal centers utilizing tartaric acid ester as a chiral auxiliary.A catalytic asymmetric 1,3-dipolar cycloaddition of nitrones possessing the N,N-diisopropylamide moiety to allylic alcohols was achieved to afford di- or trisubstituted isoxazolidines with excellent enantioselectivity of up to over 99% ee. The present asymmetric 1,3-dipolar cycloaddition was applied to the synthesis for the (2S,4R)-4-hydroxyornithine derivative.The regio- and enantioselective hetero Diels-Alder reaction of nitroso compound with dienol has been realized utilizing a catalytic amount of tartaric acid ester as a chiral auxiliary and the corresponding cycloadduct was obtained in complete regioselectivity with excellent enantioselectivity up to 84% ee.The asymmetric Diels-Alder reaction of o-quinodimethanes, generated from benzocyclobutenols in situ, with fumaric acid esters was achieved by utilizing diisopropyl (R,R)-tartrate as a chiral auxiliary to afford the corresponding optically active 1,2-cis-substituted 1-hydroxy tetrahydronaphthalene derivatives with enantioselectivity up to 83% ee.The asymmetric addition of alkynylzinc reagents, prepared in situ from dialkylzinc and 1-alkynes, to nitrones was achieved by utilizing di(t-butyl) (R,R)-tartrate as a chiral auxiliary to afford the corresponding optically active (R)-α-substituted propargylic N-hydroxylamines. By the addition of product-like N-hydroxylamine, unprecedented enhancement of enantioselectivity was observed to afford the N-hydroxylamines up to 95% ee.

为了开发一种用于构建手性分子的实用方法，我们设计了一种具有多金属中心的新型手性系统，该系统利用tart酸酯作为手性辅助辅助系统。催化不良1,3-二极极性的二极极环节，可为N-二极化的氮气提供n-二甲状腺素或型号，可为n-二异氨基甲基甲基甲基甲基甲基甲基甲基甲基甲基甲基甲基化剂量造型提供。异恶唑烷氨基烷具有极佳的对映选择性，高达99％以上。 The present asymmetric 1,3-dipolar cycloaddition was applied to the synthesis for the (2S,4R)-4-hydroxyornithine derivative.The regio- and enantioselective hetero Diels-Alder reaction of nitroso compound with dienol has been realized using a catalytic amount of tartaric acid ester as a chiral auxiliary and the corresponding cycloadduct was以极佳的a型EE的优异对映选择性以完全的区域选择性获得。o- Quinodimethanes的不对称的Diels-Alder alder alder反应是由苯二氯丁醇产生的，并在原位上产生，并通过利用二异丙基（R，R，R，R，R，R，R，R，R，R，R）来实现富马酸酯，可实现。 1,2-CIS取代的1-羟基四二乙烯衍生物具有高达83％EE的对映选择性。从dialkylzinc和1-烯烃中，对dialkylzinc和1-烯烃的不对称添加碱性（通过将niration）（通过di-di（t-butrate as a-ub a）（traly-a））（tral a）提供相应的光学活性（R）-α取代的倾斜N-羟胺。通过添加产物样的N-羟胺，观察到前所未有的对映选择性的增强可提供高达95％EE的N-羟胺。