Asymmetric Synthesis based on Carbonyl-Ene Reaction

基于羰基烯反应的不对称合成

• 批准号: 06453133
• 负责人: MIKAMI Koichi
• 金额: $ 3.52万
• 依托单位: TOKYO INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General 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/en/grant/KAKENHI-PROJECT-06453133/
• 关键词: Asymmetric ene reaction; diastereoselection; Diastereofacial selection; Binaphthol dervatives; Chiral titanium complexes; ジアステレオ面選択性; 不斉合成; イミン; アミノ酸

The purpose of this work is to develop the new method for asymmetric synthesis based on carbonyl-ene reaction. A summary of the research results is as follow :(1) Internal Asymmetric InductionThe carbonyl-ene reaction with fluoral is found to afford the erythro-trifluoromethylcsarbinol ion more thasn 90% selectivity.(2) Relative Asymmetric inductionThe carbonyl-ene reaction with b-amino aldehyde is found to exhgiobit the-diastereofacial selectivity in more than 99% selectivity. Furthermore, the reavcti0n with un-symmetricallyt substituted ene component provides only sngle regioisomer (>99% regioselectivity).(3) Enantiofacial Selective InductionThe asymmetric catalysis of carnbonyl-ene reaction catalyzed by chiral (modified) binaphthol-derived titanium complexes with prochiral carbonyl enophiles such as glyoxylate, fluoral, and conjugate ynals is found to give more than 95% enantiomeric excesses. Furthermore, the asymmetric catalytic carbonyl-ene reaction even with non-prochiral enophile such as formaldehyde afford the high levle of asymmetric induction.

本工作的目的是发展基于羰基-烯反应的不对称合成新方法。（1）内不对称诱导研究发现，羰基烯与氟醛反应生成赤型三氟甲基氰醇离子的选择性大于90%。(2)相对不对称诱导羰基-烯与b-氨基醛的反应表现出大于99%的非对映选择性。此外，用非手性取代的烯组分的反应仅提供单一的区域异构体（>99%区域选择性）。(3)对映体选择性诱导手性（修饰）联萘酚衍生的钛配合物与前手性羰基亲烯体如乙醛酸、氟醛和共轭炔醛催化羰基烯的不对称反应，发现对映体过量超过95%。此外，不对称催化的羰基-烯反应即使在非前手性亲烯体如甲醛的存在下也能提供高水平的不对称诱导。

项目成果

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

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

Koichi Mikami: "Advances in Detailed Reaction Mechanisms" JAI Press, London, 31 (1994)

Koichi Mikami：“详细反应机制的进展”JAI Press，伦敦，31（1994）

Yukihiro Motoyama: "Asymmetric Catalysis of (Hetero)Diels-Alder Cycloadditions by a Modified Binaphthol-Derived Titanium Complex" Synlett. 967-968 (1995)

Yukihiro Motoyama：“改性联萘酚衍生钛配合物对（杂）狄尔斯-桤木环加成的不对称催化”Synlett。

Masahiro Terada: "Periselective and Enantioselective Carbonyl-Ene Reaction of Isoprene with Fluoroalkyl Glyoxylate Catalyzed by MOdified Binaphthol-Titanium Complex" J. Chem. Soc. Chemical Communication. 2391-2392 (1995)

Masahiro Terada：“改性联萘酚钛配合物催化异戊二烯与乙醛酸氟烷基酯的近选择性和对映选择性羰基烯反应”J. Chem。

三上 幸一: "Stereoelectronic Rules in Addition Reactions: “Cram's Rule" in Olefinic Systems. Advances in Detailed Reaction Mechanisms, Vol 3" J. M. Coxon, ed, JAI Press: London, 34 (1994)

Koichi Mikami：“加成反应中的立体电子规则：烯烃系统中的“克拉姆规则”。详细反应机制的进展，第 3 卷”J. M. Coxon，编辑，JAI Press：伦敦，34 (1994)