以维生素B2为基础的光催化系统的基氧化,使用H2O和O2作为氧气来源
Duyi Shen1,2, Fubi Zhong1, Ting Ren1
1Key Laboratory of Life-Organic Analysis of Shandong Province, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, P. R. China.
The Journal of organic chemistry
|October 18, 2023
概括
这项研究引入了一种可持续的,无试剂的系统,使用利博弗拉四酸盐 (RFT) 和基氧化中的催化剂. 这种新的方法利用光线将基因转化为1,2-二基,氧气来源于水和空气.
科学领域:
- 可持续化学 可持续化学
- 光催化作用的光催化
- 有机合成 有机合成
背景情况:
- 为氧化反应开发可持续的催化剂至关重要.
- 使用易于获得的光催化剂和绿色氧气来源是一个有希望的策略.
- 之前的黄素化物光氧化系统通过两电子过程涉及OCl-物种.
研究的目的:
- 报告一个牺牲式无试剂系统用于基氧化.
- 为了利用 riboflavin tetraacetate (RFT) 作为一个光催化剂与共催化剂.
- 在蓝光或阳光照射下实现基氧化.
主要方法:
- 作为光催化剂使用的 рибофлавин四酸 (RFT).
- 使用了Sc ((OTf) 3和NaCl作为共催化剂.
- 在蓝光和阳光照射下进行基氧化.
主要成果:
- 通过基氧化成功生产了1,2-二基.
- 氧原子来自水和分子氧.
- 通过单个电子转移提出了一种新的Cl-/Cl•循环,其中涉及一个兴奋的[RFT-2Sc3+]*复合体.
结论:
- 开发了一种可持续的,无牺牲试剂的光催化系统,用于基氧化.
- 证明了一种新的机制,涉及在黄素中介光氧化过程中的Cl-/Cl•循环.
- 该系统使用可见光提供了一条有效的通道到1,2-二基.
更多相关视频
相关概念视频
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.2K
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.
18.2K
Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
11.7K
Alkenes can be dihydroxylated using potassium permanganate. The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
11.7K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.3K
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.
10.3K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
5.9K
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.
5.9K
Oxidative Cleavage of Alkenes: Ozonolysis
10.5K
In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
10.5K
Hydroboration-Oxidation of Alkenes
8.3K
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.
8.3K


