Chiral Dienolate Chemistry in Remote Asymmetric Induction

远程不对称感应中的手性二烯醇化学

• 批准号: 07455357
• 负责人: NAKAI Takeshi
• 金额: $ 4.8万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07455357/
• 关键词: Asymmetric Synthesis; Remote Asymmetric Induction; Chiral Dienolate; Sigmatropic Rearrangement; Cope Rearrangement; oxy-Cope Rearrangement; Pd-Catalyst; Zaragozic acid A

While the chiral auxiliary-based asymmetric induction constitutes the underlying principle most often utilized for asymmetric synthesis, the asymmetric induction at a position beyond the asymmetric environment imparted by the chiral auxiliary is, of course, extremely difficult. Conceptually, however, this problem could be solved by the proper combination in tandem of an asymmetric induction process within the asymmetric environment with an asymmetric transmission process to effect the net remote asymmetric induction.To realize this concept, we designed a general synthetic approach which relies upon the chiral dienolate chemistry for the asymmetric induction followed by the sigmatropic process for the asymmetric transmission.A summary of the research results is as follow :(1) The allylation of the dienolate derived from the chiral alpha, beta- or beta, gamma-unsaturated imide followed by the Cope rearrangement is shown to effect the net remote asymmetric induction to create a new chirality of either configuration at the gamma-position in high % de. The utility of this approach is shown in the asymmetric synthesis of the C6 side chain of zaragozic acid A.(2) The asymmetric aldol reaction of the boron dienolate derived from chiral alpha, beta- or beta, gamma-unsaturated imide followed by the siloxy-Cope rearrangement is shown to provide the gamma, delta-anti-or-syn-alpha, beta-unsaturated imide as the main product.

虽然基于手性助剂的不对称感应构成了最常用于不对称合成的基本原理，但是在超出手性助剂所赋予的不对称环境的位置处的不对称感应当然是极其困难的。然而，从概念上讲，这个问题可以通过在不对称环境下的不对称感应过程与不对称传输过程的适当组合来解决，以实现网络远程不对称感应。为了实现这个概念，我们设计了一种通用的合成方法，该方法依赖于基于手性二烯醇化学进行不对称诱导，然后进行不对称传输的σ向过程。研究结果总结如下：（1）手性α衍生的二烯醇的烯丙基化， β-或β、γ-不饱和酰亚胺随后进行Cope重排被证明会影响净远程不对称感应，从而在高％de的γ位上创建任一配置的新手性。这种方法的实用性在萨拉戈酸A的C6侧链的不对称合成中得到了体现。(2)由手性α、β-或β、γ-不饱和酰亚胺衍生的二烯醇硼的不对称羟醛反应，然后是甲硅烷氧基-Cope重排显示提供γ、δ-反-或顺-α、β-不饱和酰亚胺作为主要产物。

项目成果

中井 武: "Chiral Dienolate Chemistry in Remote Asymmetric Induction : the Allylation/Cope Rearrangement Sequence Leading to γ-Chiral α,β-Unsaturated Acid Derivatives" Tetrahedron Lett.37. 8895-8898 (1997)

Takeshi Nakai：“远程不对称诱导中的手性二烯醇化学：导致 γ-手性 α,β-不饱和酸衍生物的烯丙基化/Cope 重排序列”Tetrahedron Lett.37 (1997)。

Katsuhiko Tomooka, Atsushi Nagasawa, Shih-Yi Wei, and Takeshi Nakai: "Chiral Dienolate Chemistry in Remote Asymmetric Induction : The Asymmetric Aldol/Oxy-Cope Strategy for Asymmetric Synthesis of gamma, delta-Dichiral alpha, beta-Unsaturated Acid Derivat

Katsuhiko Tomooka、Atsushi Nagasawa、Shih-Yi Wei 和 Takeshi Nakai：“远程不对称诱导中的手性二烯醇化学：用于不对称合成 γ、δ-二手性 α、β-不饱和酸衍生物的不对称 Aldol/Oxy-Cope 策略

中井 武: "Chiral Dienolate Chemistry in Remote Asymmetric Induction : The Asymmetric Aldol/Oxy-Cope Strategy for Asymmetric Synthesis of γ,δ-Dichiral α,β-Unsaturated Acid Derivatives" Tetrahedron Lett.37. 8899-8900 (1997)

Takeshi Nakai：“远程不对称诱导中的手性二烯醇化学：用于不对称合成 γ,δ-二手性 α,β-不饱和酸衍生物的不对称 Aldol/Oxy-Cope 策略”Tetrahedron Lett.37。

中井 武: "Chiral Dienolate-Based Asymmetric synthesis : Asymmetric Allylation/Cope and Aldol/Oxy-Cope Sequences" Pacifichem'95 Abst.ORGN-100 (1995)

Takeshi Nakai：“基于手性二烯醇酯的不对称合成：不对称烯丙基化/Cope 和 Aldol/Oxy-Cope 序列” Pacifichem95 Abst.ORGN-100 (1995)

Takeshi Nakai: "Chiral Dienolate-Based Asymmetric synthesis : Asymmetric Allylation/Cope and Aldol/Oxy-Cope Sequences" Pacifichem '95 Abst.ORGN-100. (1995)

Takeshi Nakai：“基于手性二烯醇盐的不对称合成：不对称烯丙基化/Cope 和 Aldol/Oxy-Cope 序列” Pacifichem 95 Abst.ORGN-100。