一氧化碳作为关键:碳化触发了 (异质) 的迁移转换
Hefei Yang1,2, Xiao-Feng Wu1,2
1Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023 Dalian, Liaoning, China.
概括
自由基介导的一氧化碳 (CO) 插入使新的碳基功能化策略成为可能. 这种方法促进了碳链的延长,并通过激进迁移激活醇,产生有价值的化合物.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 激进化学 激进化学是什么
背景情况:
- 碳酸功能化对于合成复杂的有机分子至关重要.
- 激进反应为结合形成和功能组操纵提供了独特的途径.
- 合醇在选择性功能化方面存在挑战.
研究的目的:
- 审查激素介导的一氧化碳 (CO) 插入用于碳酸性功能化的近期进展.
- 突出CO插入在碳链延长和醇激活中的作用.
- 讨论各种激进的触发因素及其对迁移反应的影响.
主要方法:
- 对激素介导的二氧化碳插入和迁移反应的文献进行系统审查.
- 对各种激素触发物的分析 (例如,CF3,来自于diazo,以N为中心).
- 讨论对二氧化碳插入和迁移相互作用的机制性见解.
主要成果:
- 远程阿里尔/异阿里尔转移到碳基碳的证明.
- 合成有价值的1,4-二碳烯化合物和乳.
- 通过激进迁移激活具有挑战性的合醇基质.
结论:
- 激素介导的CO插入与迁移相结合,为合成功能化的支架提供了一个强大的工具.
- 温和的反应条件和广泛的基质范围是关键优势.
- 未来的方向包括扩大迁移范围,简化设计和开发非对称催化剂.
相关概念视频
Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation
4.9K
Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
The carbonyl center is activated by...
The carbonyl center is activated by...
4.9K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
20.6K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
20.6K
Carbocations
13.3K
Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
13.3K
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
2.9K
Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.
2.9K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
7.3K
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...
7.3K
Nucleophilic Aromatic Substitution: Elimination–Addition
5.0K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
5.0K


