通过宏循环支持的二铁复合体进行C-C σ-键的氧化添加和功能化
Tianchang Liu1, Ryan P Murphy1, Patrick J Carroll1
1Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Journal of the American Chemical Society
|July 26, 2022
概括
这项研究证明了使用二铁复合物激活C-C键的新型无助氧化添加反应. 这些发现允许通过催化循环高效的C-C键功能化.
科学领域:
- 有机金属化学
- 催化剂
- 合成化学
背景情况:
- 在有机合成中,C-C键的激活至关重要.
- 开发用于C-C键功能化的新催化方法仍然是一个重大挑战.
研究的目的:
- 报告第一个未经辅助的C ((sp) -C ((sp2) 和C ((sp) -C ((sp3) 键氧化添加反应的例子.
- 探索C-C西格玛键功能化的催化循环.
主要方法:
- 使用二铁复合物, (3PDI2) Fe2 ((μ-N2) ((PPh3) 2 ([Fe2N])),用于氧化添加反应.
- [Fe2N]与各种乙烯和基衍生物发生反应.
- 研究H2或HBpin的后续水功能化反应.
主要成果:
- 与二乙烯一起实现无助的C(sp) -C(sp2) 键氧化添加.
- 观察到基于固体阻碍的基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基
- 证明了C-C西格玛键的催化功能化 (化和化),再生了二铁复合体.
结论:
- 双铁复合物促进了前所未有的C-C键氧化添加反应.
- 这项工作为C-C西格玛键功能化提供了新的催化途径,提供了热力学上有利的产物.
相关概念视频
02:04Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
6.1K
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.
6.1K
01:27Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
2.3K
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
2.3K
01:16Cycloaddition Reactions: Overview
2.7K
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.
2.7K
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.7K
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.
18.7K
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.7K
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.
10.7K
03:08Hydroboration-Oxidation of Alkenes
8.8K
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.
8.8K