Catalytic Asymmetric Synthesis of Fluorine-containing Substrates (Flustrates)

含氟底物（Flustrates）的催化不对称合成

• 批准号: 06555271
• 负责人: MIKAMI Koichi
• 金额: $ 3.71万
• 依托单位: TOKYO INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06555271/
• 关键词: Asymmetric ene reaction; Asymmetric aldol reaction; Asymmetric Diels-Alder reaction; Binaphthol derivatives; Chiral titanium complexes; Fluoral; diastereoselection; 反強誘電性液晶; 光学活性含フッ素有機化合物; エナンチオ選択性; 不斉炭素・炭素結合生成反応

The purpose of this work is to develop the method for catalytic asymmetric synthesis of fluorine-containing substrates (flustrates) based on catalytic asymmetric carbonyl-ene, aldol, and Diels-Alder reactions with prochiral fluoral, difluoroacetaldehyde, and so forth. A summary of the research results is as follow :(1) Catalytic Asymmetric Ene Reaction with FluoralThe carbonyl-ene reaction with fluoral is found to afford the erythro-trifluoromethylcarbinol in more than 90% enantioselectivity by the asymmetric catalysis of chiral binaphthol-derived titanium complexes.(2) Catalytic Asymmetric Aldol Reaction with FluoralThe Mukaiyama aldol reaction with fluoral and difluoroacetaldehyde is found to afford the fluorine containing aldol products in more than 90% enantioselectivity by the asymmetric catalysis of chiral binaphthol-derived titanium complexes.(3) Catalytic Asymmetric Diels-Alder Reaction with FluoralThe asymmetric catalysis of Diels-Alder reaction with fluoral is so far unsuccessful even by the catalysis of chiral modified binaphthol-derived titanium complexes.

本工作的目的是发展一种催化不对称合成含氟底物（flustrates）的方法，该方法基于催化不对称羰基烯、羟醛和Diels-Alder反应与前手性氟醛、二氟乙醛等的反应。主要研究结果如下：（1）氟醛催化不对称烯反应在手性联萘酚钛配合物的不对称催化作用下，羰基与氟醛的不对称烯反应得到了90%以上的赤型三氟甲基甲醇。(2)手性联萘酚衍生的钛配合物的不对称催化下，向山醇醛与氟醛和二氟乙醛的不对称羟醛缩合反应，对映选择性大于90%。(3)含氟醛的催化不对称Diels-Alder反应含氟醛的催化不对称Diels-Alder反应迄今为止，即使是手性修饰的联萘酚衍生的钛配合物的催化也是不成功的。

项目成果

Mikami Koichi: "Asymmetric Catalysis of Glyoxylate-Ene Reaction and Related Reactions" Adv.Cat.Processes.1. 123-149 (1995)

Mikami Koichi：“乙醛酸-烯反应及相关反应的不对称催化”Adv.Cat.Processes.1。

Mikami Koichi: "Asymmetric Catalysis of Carbonyl-Ene Reactions and Related Carbon-carbon Forming Reactionsi" Pure & Appl.Chem.(in press).

三上浩一：“羰基烯反应及相关碳碳形成反应的不对称催化”纯

Koichi Mikami: "Asymmetric Catalysis of Carbonyl-Ene and Aldol Reactions with Fluoral by Chiral Binaphthol-Derived Titanium Complex" Tetrahedron. 52. 85-96 (1996)

Koichi Mikami：“手性联萘酚衍生的钛配合物对羰基烯和羟醛与氟的反应的不对称催化”四面体。

Koichi Mikami: "Advances in Asymmetric Synthesis" JAZ Press, London, 35 (1994)

Koichi Mikami：“不对称合成的进展”JAZ Press，伦敦，35 (1994)

Koichi Mikami: "Advances in Catalytic Processes" JAZ Press, London, 26 (1995)

Koichi Mikami：“催化过程的进展”JAZ Press，伦敦，26 (1995)