使用水作为氧原子的来源,通过介导的电化学氧化硫乙烯
Md Asmaul Hoque1, Tianxiao Jiang1, Darren L Poole2
1Department of Chemistry, University of Wisconsin─Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Journal of the American Chemical Society
|July 23, 2024
概括
催化剂使得选择性电化学氧化硫乙烯成为硫氧化物,使用水作为氧源. 这种更环保的方法避免使用苛刻的试剂,并为制药合成提供广泛的应用.
科学领域:
- 化学学
- 电化学
- 有机合成
背景情况:
- 氧原子转移反应在合成化学中至关重要,但通常依赖于危险的试剂.
- 电化学方法提供了一个可持续的替代方案,利用水作为直接或间接电解的氧气来源.
研究的目的:
- 开发一种高效和选择性的电化学方法来氧化以硫化.
- 探索色和相关化合物作为这种转换的分子电催化剂.
主要方法:
- 使用基于甲的介质,电化学氧化硫乙烯.
- 通过质子合电子转移产生高价值的氧物种 (MnIV-OH,MnVO).
- 与直接电解和化物介导的电化学氧化进行比较
- 开发一个用于催化剂优化的电化学并行选平台.
主要成果:
- 催化剂可以选择性地将硫乙烯氧化为硫氧化物,而过氧化为硫.
- 与直接电解相比,Mn介导的过程在较低的电位下运行.
- 与直接电解相比,观察到基质范围和功能组耐受性得到改善.
- 可调节的Mn基调剂的性能优于化物介导的电解.
结论:
- 甲电催化剂提供了可持续和高效的硫乙烯氧化途径.
- 这种方法在选择性,效率和适用性方面为合成硫化物提供了优势,特别是对于药物相关的化合物.
相关概念视频
Radical Oxidation of Allylic and Benzylic Alcohols
1.9K
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
1.9K
Preparation and Reactions of Thiols
6.1K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
6.1K
Preparation and Reactions of Sulfides
4.8K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
4.8K
Oxidation of Alcohols
12.9K
In this lesson, the oxidation of alcohols is discussed in depth. The various reagents used for oxidation of primary and secondary alcohols are detailed, and their mechanism of action is provided.
The process of oxidation in a chemical reaction is observed in any of the three forms:
The process of oxidation in a chemical reaction is observed in any of the three forms:
12.9K
Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
11.2K
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.
11.2K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.0K
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.
10.0K


