在铁催化中依赖基质的双态活性 [2+2] 循环添加反应
Lianrui Hu1,2, Hui Chen1
1Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.
Journal of the American Chemical Society
|October 25, 2017
概括
铁催化使得通过阶段性途径挑战 [2+2] 循环添加. 这项研究揭示了铁催化中的基质依赖的双态反应性,阐明了基本的反应机制.
科学领域:
- 有机金属化学
- 催化剂
- 反应机制
背景情况:
- 铁催化 [2+2] 循环添加为动力阻碍协同反应提供了一种渐进的替代方案.
- 控制这些铁催化过程的基本反应性范式在很大程度上仍未定义.
研究的目的:
- 在铁催化 [2+2] 循环添加反应中阐明基质依赖的反应场景.
- 澄清氧化还原活性联体和电子状态在催化循环中的作用.
主要方法:
- 高级综合CASPT2/DFT计算建模.
- 分析铁催化过程中的关键碳-碳合步骤.
- 研究金属循环中间体和还原性消除途径.
主要成果:
- 在关键C-C合步骤中确定了前所未有的基质依赖的双态反应场景.
- 单烯和单烯/1,3-二烯基底表现出不同的反应模式.
- 反氧活性联体促进Fe (III) /Fe (I) 减少性消除途径,比Fe (II) /Fe (0) 更容易获得.
结论:
- 该研究澄清了铁催化 [2+2] 循环添加的机制,突出了基质对反应性的影响.
- 提高旋转状态过渡效率提供了一种在交叉循环添加中提高反应性的策略.
- 一开始的多参考方法对于复杂的开铁催化是有效的.
相关概念视频
Cycloaddition Reactions: MO Requirements for Thermal Activation
4.7K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
4.7K
Cycloaddition Reactions: Overview
3.6K
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.
3.6K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.8K
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.
2.8K
Pericyclic Reactions: Introduction
10.6K
Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
10.6K
Introduction to Electrophilic Addition Reactions of Alkenes
10.7K
The double bond in a simple, unconjugated alkene is a region of high electron density that can act as a weak base or a nucleophile. The filled π orbital (HOMO) of the double bond can interact with the empty LUMO of an electrophile. A bonding interaction occurs when the electrophile attacks between the two carbons; the electrophile then accepts a pair of electrons from the π bond and undergoes addition across the double bond, yielding a single product.
Addition and elimination...
Addition and elimination...
10.7K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
17.6K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
17.6K


