多铜集群使的氧化宏循环 (OxPM) 成为可能
Anna Libman1, Mor Ben-Lulu1, Eden Gaster1
1Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel.
Journal of the American Chemical Society
|September 18, 2023
概括
研究人员开发了一种新的仿生方法,使用多铜 (II) 集群合成复杂的宏环,包括菌素环模型. 这种有效的方法克服了创造这些重要抗生素结构的挑战.
科学领域:
- 有机化学
- 医学化学
- 生物化学
背景情况:
- 甘油抗生素如万科米通过酶的氧化大循环合成.
- 现有的仿生方法对这种转化不够简单或节省步骤.
研究的目的:
- 开发一种高效且节省步骤的生物模拟方法,用于合成二桥和二以太结合的宏环.
- 证明多铜 (II) 集群在催化具有挑战性的宏循环反应中的实用性.
主要方法:
- 使用多铜 (II) 集群促进分子内氧化合.
- 开发了宏环的选择性合成条件.
- 合成的万科米辛环模型和阿里洛米辛循环核心.
主要成果:
- 实现了二桥和二以太结合的大环的高效合成.
- 证明了多铜 (II) 集群能够化二醇并促进分子内合.
- 成功合成复杂的抗生素宏环模型.
结论:
- 多铜 (II) 集群为生物模拟宏循环提供了强大的催化系统.
- 这项技术有助于组装具有挑战性的复杂抗生素宏环.
- 铜集群可以催化超出较小的金属催化剂范围的氧化还原转换.
相关概念视频
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
2.6K
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
2.6K
Preparation of Epoxides
7.8K
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of...
7.8K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
Cycloaddition Reactions: Overview
2.6K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.6K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.1K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.1K
Olefin Metathesis Polymerization: Overview
2.2K
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.2K


![[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)