一个高张力Al-Al σ-键在Dianionic类型的氧化分子激活
1Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 637371, Singapore.
Journal of the American Chemical Society
|October 26, 2021
概括
研究人员合成了一种具有紧张的Al-Al西格玛键的新型二氧化分子. 这种独特的化合物很容易与不和基质反应,形成各种异环化合物并激活C-C键.
科学领域:
- 有机金属化学
- 主要组化学
- 合成化学
背景情况:
- 的高电阳性使得二离子Al-Al西格玛键的构造具有挑战性.
- 之前的研究没有报告具有二性Al-Al西格玛键的稳定分子.
研究的目的:
- 报告第一个DianionicDialane分子的合成.
- 描述合成的迪兰的结构和结合.
- 探索二基与不和基质的反应性.
主要方法:
- 基于Al2O三环支架的新型二氧化支架的合成.
- 使用光谱分析和X射线晶体学进行结构阐明.
- 计算研究以了解结合和反应机制.
主要成果:
- 成功合成并表征了具有紧张Al-Al西格玛键的二氧化二氧化 (2).
- 证明了 (2) 与异化物,乙烯和子的反应性,形成四个和五个成员的异环 (3-5).
- 由 (2) 与酸的反应形成一个七个成员的异环 (6) ,涉及C-C合.
- 通过 (2) 激活双烯的C-C键,产生二替代的基[8]烯衍生物 (7).
结论:
- 已经合成了第一个具有紧张Al-Al西格玛键的DianionicDialane.
- 迪兰具有多功能反应性,可形成多种异环结构.
- 这些发现开辟了主要组化学和新型有机化合物的合成的新途径.
更多相关视频
相关概念视频
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
11.1K
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.
11.1K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
6.6K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
6.6K
Hydroboration-Oxidation of Alkenes
9.3K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
9.3K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
6.3K
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
6.3K
Electrophilic Addition to Alkynes: Halogenation
8.9K
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
8.9K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
11.0K
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.
11.0K


