控制自行车结构的激序级循环中的反选择性和反选择性
Congzhe Zhang1, Duo-Sheng Wang1, Wan-Chen Cindy Lee1
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States.
Journal of the American Chemical Society
|July 14, 2021
概括
这项研究引入了一种新型的催化方法,用于不对称的激素循环,使复杂分子合成中能够精确控制反选择性和异选择性. 基催化方法可以构建具有高立体化学精度的复杂多环结构.
科学领域:
- 有机化学
- 催化剂
- 合成方法
背景情况:
- 激序级循环化是合成多环分子的强大工具.
- 控制激素级循环中的酶选择性仍然是一个重大挑战.
- 金属催化 (MRC) 提供了不对称转换的潜力.
研究的目的:
- 开发第一个金属基催化 (MRC) 系统,用于反选择性和异选择性基级联循环.
- 建立以为基础的催化系统,以使1,6-因与二化合物进行不对称的激素循环.
主要方法:
- 开发一种使用D2对称的性胺胺作为配体的基于Co2的催化系统.
- 在温和条件下与二化合物进行 1,6-因的不对称基循环.
- 结合计算和实验研究来阐明反应机制.
主要成果:
- 成功构建了多替代环融合四原体,其中有三个连续的立体中心,包括两个全碳四度中心.
- 在激素级联过程中获得的高产量和优秀的立体选择性.
- 一个阶段性基因机制的识别,其中涉及辅助的C中心基因中间体 (α-, β-, γ-, ε-金属基因).
结论:
- 在激素级联反应中,Co (II) -MRC系统提供了一种控制异构选择性和异构选择性的通用方法.
- 开发的方法可实现对抗丰富的环聚合四酸的不对称合成,这些四酸是进一步立体选择性合成的有价值的中间体.
- 这项研究突显了MRC在推进非对称基化学方面的潜力.
相关概念视频
Radical Halogenation: Stereochemistry
4.0K
Stereochemistry is the study of the different spatial arrangements of atoms in a given molecule. The stereochemistry of radical halogenations can be understood from three different situations:
Halogenation to form a new chiral center:
Halogenation to form a new chiral center:
4.0K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
4.9K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
4.9K
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
4.3K
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
4.3K
Radical Anti-Markovnikov Addition to Alkenes: Overview
3.7K
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
3.7K
Radical Reactivity: Intramolecular vs Intermolecular
1.8K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
1.8K
Radical Reactivity: Steric Effects
2.0K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
Along with electronic...
2.0K

![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
