通过使用可见光,包括一个太阳照明的单金属铜氧复合体对基的光氧氧化
Daniel L Nascimento1, David Gygi1, Matthew C Drummer1
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
Journal of the American Chemical Society
|October 8, 2024
概括
这项研究使用可见光对铜复合物进行氧化. 一种新型复合物激活中的C-H键,在温和条件下产生有价值的氧化物.
科学领域:
- 催化剂
- 摄影化学
- 有机金属化学
背景情况:
- 碳化合物氧化对于合成有价值的化学物质如酒精和非常重要.
- 单金属铜氧物种是重要的生物化剂,但合成模型在高C-H键解离能量下扎.
研究的目的:
- 研究铜复合物的光化学作用,以激活中的C-H键.
- 开发能够在温和条件下与碳化合物反应的合成模型化合物.
主要方法:
- 使用酸协调的单金属铜 (pyrazolyl) 复合物.
- 在可见光下,研究了C1-C6基的光化学 (BDE≥93kcal/mol).
- 使用光晶体学和机理学研究来阐明反应途径.
主要成果:
- 通过使用高氧化铜复合物 (Cu-3) 来实现乙 (15-30%的产量) 和甲到甲醇的光氧化.
- 证明了连接物修饰调整了氧化还原潜力和反应选择性.
- 在一个阳光照明条件下展示了光化学的可行性.
结论:
- 开发了一种用铜催化的光反系统,用于使用可见光激活中强大的C-H键.
- 该系统产生强大的铜-氧基中间体,使原子抽象成为可能.
- 这项工作在环境条件下为氧化碳提供了可持续的途径.
更多相关视频
相关概念视频
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
9.9K
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.
9.9K
Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
11.0K
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.
11.0K
Oxidative Cleavage of Alkenes: Ozonolysis
10.0K
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.
10.0K
Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
5.7K
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.
5.7K
Oxymercuration-Reduction of Alkenes
7.5K
Oxymercuration–reduction of alkenes is one of the major reactions converting alkenes to alcohols. It involves the hydration of alkenes with mercuric acetate in a mixture of tetrahydrofuran and water, forming an organomercury adduct. This is followed by a demercuration step in which the adduct is reduced to an alcohol using sodium borohydride.
7.5K
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)

