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.

以2，5-二取代吡咯烷为手性助剂进行了有效的不对称反应和立体选择性反应。当使用相应的锆烯醇类化合物时，这些酰胺类烯醇酸酯与醛的羟醛缩合反应具有很高的非对映(&gt；60：1)和非对映(&gt；95%)选择性。由(E)-烷氧乙酰酰胺衍生的锆烯醇酸盐在其[2，3]Wittig重排反应中表现出高水平的非对映(&gt；28：1)和非对映(&gt；95%)选择性。(E)-和lt；α&gt；-烯氧基乙酸乙酸酯的[2，3]Wittig重排反应也具有同步非对映选择性(&gt；50：1)、高水平的手性转移(-100%)和(Z)-双键的排外形成。这种[2，3]Wittig重排反应和Peterson反应的结合为(E，Z)-和(Z，Z)-二烯提供了一种高度立体选择性的方法。此外，与通常的[3，3]S型重排不同的是，锆离子介导的烯酸克莱森重排反应是通过船形过渡态进行的，不同于通常的[3，3]S型重排反应是通过椅子状过渡态进行的。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)

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。

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。

内山春美: Chemistry Letters. 351-354 (1987)

内山晴美：化学快报 351-354 (1987)