铁催化型立体合型1,4-化结合二烯的化化
Wei Sun1, Meng-Yang Hu1, Zhan-Sheng Lu1
1Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.
Angewandte Chemie (International ed. in English)
|November 7, 2023
概括
这项研究引入了一种铁催化方法,用于对二烯的立体融合1,4-基化,有效地产生Z-基. 这种新的方法通过通过固体阻碍催化剂控制基质协调来实现高选择性.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 有机金属化学 有机金属化学
背景情况:
- 立体融合合成对于创建单个立体同位素产品至关重要.
- 在有机合成中,将E/Z烯混合物转化为特定的配置仍然是一个重大挑战.
研究的目的:
- 开发一种对结合型二烯的立体融合型1,4-基化方法.
- 合成具有高区域选择性和绝对立体选择性的Z-基西兰.
主要方法:
- 铁催化化反应.
- 使用易于获得的联二烯的E/Z混合物.
- 使用α-二胺基改性铁催化剂.
主要成果:
- 从E/Z二烯混合物中实现了Z-基西兰的立体融合合成.
- 在转型过程中表现出高的区域选择性和独特的立体选择性.
- 提出了一种两电子氧化还原机制,其中涉及一种经过绝缘控制的抗π-烯酸铁中间体.
结论:
- 开发的铁催化反应提供了一个有效的途径到Z-allylsilanes.
- 催化剂的设计,特别是连接体的硬质体质量,是实现立体选择性的关键.
- 提出的机制在相关反应中不同于激素或金属化物通路.
相关概念视频
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01:16[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
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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.
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Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
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01:28Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
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The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
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01:29Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
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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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01:28Stability of Conjugated Dienes
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Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
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02:34Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
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The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
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