Developemt of Asymmetric Carbanion Rearrangements with High Stereoselection

高立体选择不对称碳负离子重排的研究

• 批准号: 60470092
• 负责人: NAKAI Takeshi
• 金额: $ 2.82万
• 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: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470092/
• 关键词: Asymmetric Synthesis; [2,3]-Wittig Rearrangement; Chiral Enolate; <alpha> -Hydroxy Carboxylic Acid; 8-Phenylmenthol; Diastereofacial Selection; α-ヒドロキシカルボン酸

The main results of this project are summarized as follows.(1) Asymmetric [2,3]-Wittig rearrangement involving chiral lithium and potassium azaenolate termini generated from chiral 2-oxazolines have been investigated. We found that these rearrangements provided relatively high optical yields (78-95% ee). During these studies, we have observed interesting influences of the countercation (Li vs. K) and their complexation with a crown ether. Furthermore, the asymmetric reaction has successfully been applied to the chiral synthesis of unnatural verrucarinolactone.(2) Asymmetric [2,3]-Wittig rearrangement involving chiral amide Li- and Zr( <IV> )-enolate termini generated from the prolinol- and valinol-derived amide systems has been studied. Unfortunately, these asymmetric variants have been found to provide only moderate levels of asymmetric induction. Interestingly, however, the Zr-enolate variant has been shown to the opposite sense of diastereofacial selection to that of the Li-enolate … More counterpart.(3) Asymmetric [2,3]-Wittig rearrangement involving chiral ester enolate termini generated from the 8-phenylmenthol-derived chiral ester system has been investigated in details. First, we have found that the Li-enolate rearrangement provides an extremely high optical yields (>95% ee) along with a high erythro-selectivity (>90%). Thus, this type of asymmetric rearrangement offers an efficient method for chiral synthesis of <alpha> -hydroxy- <beta> -alkyl carboxylic acid derivatives. Its efficiency has been demonstrated within the simple chiral synthesis of verrucarinolactone. Second, the rearrangement involving Ti( <IV> )- and Sn( <IV> )-enolates generated from the silyl enol ether via transmetalation has been found to exhibit very low levels of asymmetric induction. Third, the rearrangement involving Zr( <IV> )-enolate generated from the Li-enolate via transmetalation, by contrast, provides a high optical yield comparable to that of the Li-enolate counterpart.On the basis of these results described above, we have discussed and elucidated the structures of the metal enolates involved in the [2,3]-Wittig rearrangements. Less

该项目的主要结果总结如下。（1）已经研究了涉及手性2-恶唑素产生的手性锂和阿Zaenaly末端的不对称[2,3] - wittig重排。我们发现这些重排提供了相对较高的光学产量（78-95％EE）。在这些研究中，我们观察到反遭受反应的有趣影响（Li vs. K）及其与冠状以太的络合。此外，不对称反应已成功地应用于非自然的紫杉醇分子的手性合成。（2）不对称[2,3] - wittig重排涉及手性酰胺酰胺li-和Zr（<iv>） - 二酸酯 - 二酸酯 - 二酸酯末端是从沿垂钙酚 - 丙醇 - 胺化系统中产生的。不幸的是，这些不对称变体仅提供中等水平的不对称诱导。然而，有趣的是，ZR-二元组的变体已显示出与锂二酸盐的相反意义相反的感觉。（3）不对称的[2,3] - wittig涉及的手性酯酯烯酸酯糖化末端涉及的8-苯基省chiralmentholmentholmentholmenthol的chiriral ester ester ester eral termini已对其进行了研究。首先，我们发现锂二方重排提供了极高的光学产率（> 95％EE）以及高红细胞选择性（> 90％）。这是这种非对称重排提供了一种有效的方法，用于<Alpha> -Hydroxy- <beta> -alkyl羧酸衍生物的手性合成。它的效率已在简单的紫杉醇甲酮合成中得到证明。其次，发现涉及Ti（<iv>） - 和Sn（<iv>） - 通过翻译产生的烯醇化的重排（<iv>） - 烯酚表现出非常低的不对称诱导水平。第三，相比之下，通过翻译产生的Zr（<iv>） - 二酸盐的重排提供了与上述结果的基础相当的高光学屈服，我们已经讨论并阐明了[2,3,3] -wittig contrangements-witig andermements的基础。较少的

项目成果

Osamu Takahashi: Chemistry Letters. 69-72 (1987)

高桥修：化学快报。

Takeshi Nakai: Chemical Reviews. 86. 885-902 (1986)

中井武：化学评论。

Koichi Mikami: Chemistry Letters. 1729-1732 (1985)

三上浩一：化学快报。

中井武: PETROTECH. 10. 58-64 (1987)

中井武：《石油技术》。10. 58-64 (1987)

Koichi Mikami: Tetrahedron Letters. 25. 6011-6014 (1984)

三上浩一：四面体字母。