Pd/smNBE(D) 化学与氨基组相遇:催化循环和化学选择性
Bo-Sheng Zhang1, Yong-Min Liang2
1College of Chemistry and Chemical Engineering, Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Northwest Normal University, Lanzhou 730070, China.
这项研究克服了/诺伯 (Pd/NBE) 化学中的一个关键局限性,使得ortho-aminoaryl化物能够发挥功能. 新的策略允许C-H功能化和随后的C-N键形成,扩大合成应用.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- /诺伯 (Pd/NBE) 化学是通过C-H功能化和交叉合来实现多功能化的强大工具.
- "形效应"和"形约束"原则控制Pd/NBE反应,通常需要形替代的烯化物.
- 一个持久的局限性是Pd/NBE化学无法容忍由于协调和核友好性问题而在正体位置的氨基群.
研究的目的:
- 开发新的Pd/NBE策略来合成 орто-aminoaryl化物,克服该领域的一个重大局限性.
- 探索新的催化途径,使C-H功能化和随后的C-N键形成在正氨基基团的存在下.
- 证明这些新方法在各种C-H功能化反应中的广泛适用性以及它们在合成有价值化合物的实用性.
主要方法:
- 采用了对直接催化作用的固体阻碍,以致于诺伯介导的形C-H功能化,防止了直接的C-N合.
- 采用惰性C-N或N-S键裂解策略,以促进C-N键构造的norbornene挤出和随后的alkyne插入.
- 解决了通过β-碳消除优先考虑与自由N-H组相结合的C-N合而不是norbornene挤出的挑战.
- 进行密度函数理论 (DFT) 计算,以阐明反应机制和选择性.
主要成果:
- 成功开发了使Pd/NBE化学在ortho-aminoaryl化物上的战略,克服了以前的局限性.
- 证明了开发的方法对各种C-H功能化的适用性,包括氨基化,基化,基化,糖基化,基化和碳基化.
- 通过制备重要的制药剂和多功能构建块来验证合成实用性.
- DFT计算为观察到的高选择性提供了机械洞察力.
结论:
- 开发的Pd/NBE(D) 化学有效地克服了烯化物中正氨基基组耐受性的挑战.
- 这些新的策略提供了广泛的功能化化合物,显著扩大了Pd/NBE应用的范围.
- 该方法强大,适用于复杂分子合成,为药物化学和材料科学提供有价值的工具.
更多相关视频
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
08:25Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Catalysis
SN2 Reaction: Transition State
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
SN2 Reaction: Stereochemistry
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
SN2 Reaction: Kinetics
In a chemical reaction, a relationship exists between the concentration of reactants and the rate at which the reaction proceeds. The study to measure this relationship is known as the kinetics of a chemical reaction. Kinetic studies are used to deduce the rate law of a chemical reaction, which provides information about the species involved during the transition state of the rate-determining step. Thus, kinetic studies help to derive the mechanism of a...
