使用数据科学指导化基体范围分析与酸盐作为酒精衍生基源的Ni/光电化交叉合
Stavros K Kariofillis1,2, Shutian Jiang1, Andrzej M Żurański1
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Journal of the American Chemical Society
|January 5, 2022
概括
这项研究引入了一种新的/光催化方法,用于使用酒精衍生基形成C(sp2) -C(sp3). 用数据科学技术系统评估基质范围,并与现有方法比较反应性趋势.
科学领域:
- 有机化学
- 催化剂
- 摄影化学
背景情况:
- /光氧化催化是形成C(sp2) -C(sp3) 键的关键方法.
- 目前的方法通常使用化,但范围评估不一致,难以选择方法.
研究的目的:
- 开发使用酒精衍生基的Ni/光氧催化化.
- 应用数据科学来系统地划分和比较Ni/photoredox方法.
主要方法:
- 使用甲二乙醇作为Ni/光电氧催化中的酒精基源.
- 使用DFT特征化,维度缩小和等级聚类来分析化化学空间.
- 综合数据科学,将新方法的范围与已公布的Ni/photoredox反应进行比较.
主要成果:
- 证明了化的成功 (二甲基) 甲基化和基化,包括纤维酸的晚期衍生物化.
- 创建了一个代表性的化集合,并绘制出已公布的方法覆盖面和产量.
- 使用机器学习识别稀疏覆盖面和量化反应趋势.
结论:
- 开发的Ni/photoredox方法为C(sp2) -C(sp3) 键形成提供了新的途径.
- 数据科学为催化过程中的系统范围分析和比较提供了强大的框架.
- 这种方法可以更好地了解功能组的兼容性和反应性趋势.
更多相关视频
相关概念视频
Nucleophilic Aromatic Substitution: Elimination–Addition
4.2K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.2K
Radical Substitution: Allylic Bromination
5.6K
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
5.6K
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
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
4.1K
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
4.1K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
19.1K
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.
19.1K
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
4.1K
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
4.1K
![[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)

