Development and Application of <C_2> -Symmetrically Substituted Pyrrolidine Chiral Auxiliaries

<C_2>-对称取代吡咯烷手性助剂的开发与应用

• 批准号: 59470020
• 负责人: YAMAGUCHI Masaru
• 金额: $ 4.61万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1984
• 资助国家: 日本
• 起止时间: 1984 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-59470020/
• 关键词: 2,5-Disubstituted Pyrrolidines; <C_2> -Symmetry; Asymmetric Reaction; [2,3]Wittig Rearrangement; 立体選択的反応; 〔2,3〕Wittig転位

Effective asymmetric reactions with 2,5-disubstituted pyrrolidines as chiral auxiliaries and related stereoselective reactions were developed.The aldol condensation of the amide enolates derived from these amides, with aldehydes proceeded with high diastereo (>60:1) and diastereoface (>95% de) selectivities, when the corresponding zirconium enolates were used. Zirconium enolates derived from (E)-alkenyloxyacetyl amides, exhibited high level of syn-diastereo (>28:1) and diastereoface (>95% de) selectivities in their [2,3]Wittig rearrangement reaction. Zirconium mediated [2,3]Wittig rearrangement of (E)- <alpha> -alkenyloxyacetic acid esters was also performed with syn-diastereoselectivity (>50:1), high level of chirality transfer (-100%), and exclusive formation of (Z)-double bond. A combination of this [2,3]Wittig rearrangement reaction and Peterson reaction provided a highly stereoselective approach to (E,Z)- and (Z,Z)-dienes. Further, zirconium mediated enolate Claisen rearrangement was found to proceed through a boat-like transition state, differing from the usual [3,3]sigmatropic rearrangements which proceed through a chair-like transition state.Some of these reactions were applied to the synthesis of natural products. Informations obtained through these studies are considered to contribute to the development of acyclic stereocontrol.

开发了以 2,5-二取代吡咯烷作为手性助剂的有效不对称反应和相关的立体选择性反应。衍生自这些酰胺的酰胺烯醇化物与醛的醇醛缩合以高非对映体 (>60:1) 和非对映面 (>95%) 进行。 de) 当使用相应的烯醇化锆时的选择性。衍生自 (E)-烯氧基乙酰酰胺的锆烯醇化物在 [2,3]Wittig 重排反应中表现出高水平的顺式非对映体 (>28:1) 和非对映体面 (>95% de) 选择性。锆介导的 (E)-<α>-烯氧基乙酸酯的 [2,3]Wittig 重排也具有顺式非对映选择性 (>50:1)、高水平的手性转移 (-100%) 和排他性形成(Z)-双键。这种 [2,3]Wittig 重排反应和 Peterson 反应的组合提供了一种对 (E,Z)- 和 (Z,Z)-二烯具有高度立体选择性的方法。此外，发现锆介导的烯醇化物克莱森重排通过船状过渡态进行，与通常通过椅状过渡态进行的[3,3]σ重排不同。其中一些反应被应用于合成天然产品。通过这些研究获得的信息被认为有助于非循环立体控制的发展。

项目成果

香月勗: Chemistry Letters.

一树：化学快报。

内川昌子: Tetrahedron Letters. 27. 4581-4582 (1986)

内川雅子：四面体信件 27. 4581-4582 (1986)

Satoru Kuroda: "Stereoselective Synthesis of (2E,4Z)-Dien-1-ols; Key Intermediates for Synthesis of Sex Pheromones of Silk Worm and Grape Vine Moth" Tetrahedron Letters. 28. (1987)

Satoru Kuroda：“(2E,4Z)-Dien-1-ols 的立体选择性合成；蚕和葡萄蛾性信息素合成的关键中间体”四面体字母。

Masako Uchikawa: "Asymmetric [2,3]Wittig Rearrangement of 2'-Alkenyloxyacetamide Bearing trans-2,5-Bis(methoxymethoxymethyl)pyrrolidine Moiety as a Chiral Auxiliary" Tetrahedron Letters. 27. 4577-4580 (1986)

Masako Uchikawa：“带有反式 2,5-双（甲氧基甲氧基甲基）吡咯烷部分作为手性辅助的 2-烯氧基乙酰胺的不对称 [2,3]Wittig 重排”四面体字母。

Tsutomu Katsuki: "Asymmetric Aldol Reaction of Amide Enolates Bearing trans-2,5-Disubstituted Pyrrolidines as Chiral Auxiliaries" Tetrahedron Letters. 26. 5807-5810 (1985)

Tsutomu Katsuki：“带有反式 2,5-二取代吡咯烷作为手性助剂的酰胺烯醇化物的不对称羟醛反应”四面体字母。