控制的自我组装多个二聚体的宏环波乙烯,由两个奇拉单元组成
Suguru Ito1, Kosuke Ono, Nobuharu Iwasawa
1Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan.
Journal of the American Chemical Society
|August 14, 2012
概括
研究人员开发了一种使用自组装合成宏环波乙烯的方法. 这种技术成功地制造了五种异构体中的四种,其中三种可以在纯净的形式中获得.
科学领域:
- 有机化学 有机化学
- 超分子化学 超分子化学
- 化学 化学
背景情况:
- 宏循环乙烯 Ester 是重要的合成标.
- 在宏观循环合成中控制立体化学仍然具有挑战性.
研究的目的:
- 开发一种自组装方法,用于对宏循环乙烯 Ester 的控制合成.
- 为了在宏观循环形成中实现高产量和多重选择性.
- 为了使能合成对抗纯宏环波乙烯的乙烯基.
主要方法:
- 采用两个性元件的自我组装.
- 优化对二聚体控制的反应条件.
- 采用构建块的不同奇拉性组合.
主要成果:
- 对五种可能的宏环乙烯 Ester 的四种异构体的受控构造.
- 在合成的二聚体聚合物中获得了高产量.
- 三种二聚体被成功合成为enantiopure形式.
- 已证明适用于具有多种二博酸部分的三组分自我组装的酸纯宏循环.
结论:
- 开发的自组装方法提供了一个可靠的途径,以立体化学定义的宏循环乙酸.
- 这种方法在控制 diastereoselectivity 和 enantiopurity 方面提供了灵活性.
- 这种方法是多功能和适用于复杂的多组件系统.
相关概念视频
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
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Regioselectivity and Stereochemistry of Hydroboration
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
Prochirality
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