在Rh(III) 催化 [3 + 3] 螺旋循环中,3--3-氧化因多林与乙烯碳酸盐作为三原子单元
1School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou 221116, Jiangsu, China. hsjin@jsnu.edu.cn.
Organic & biomolecular chemistry
|June 20, 2023
概括
一种新型的Rh(III) 催化反应有效地从3 - -3 - 氧化英多林中合成螺旋染色体. 这种原子经济的C-H激活途径使用乙烯碳酸作为三原子合成子来构建复杂的螺旋热环.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 异环化学 异环化学
背景情况:
- 伊索因多林衍生物是药物化学中的重要支架.
- 螺旋铁环具有独特的三维结构,具有多样化的生物活动.
- 构建复杂的螺旋环框架的高效合成方法非常受欢迎.
研究的目的:
- 开发一种新且高效的方法来合成由异印林衍生的螺旋色素.
- 为了探索3--3-氧化英多林作为螺旋循环反应中的构建块的实用性.
- 建立使用乙烯碳酸的Rh(III) 催化取消策略.
主要方法:
- 采用了Rh(III) 催化 [3+3] 无效反应.
- 作为起始材料使用了3-aryl-3-hydroxyisoindolinones.
- 乙烯碳酸盐作为合伙伴,通过脱碳化作用作为C-C-O三原子合成子.
主要成果:
- 这种反应有效地产生了来自isoindolinone的spiroisochromenes.
- 该过程在温和的反应条件下进行.
- 使用了C-H激活途径,证明了原子经济.
- 这代表了使用这些特定构件的这种螺旋热环的首次报告合成.
结论:
- 一种新的Rh (III) 催化螺旋循环反应已经成功开发出来.
- 该方法提供了一条有效的途径,以获得有价值的异印林衍生螺旋色素.
- 这项工作扩大了合成工具箱,用于构建复杂的螺旋环化合物.
相关概念视频
Thermal Electrocyclic Reactions: Stereochemistry
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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
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Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
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