![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
通过Pd(0) /Chiral酸共催化方式对Enyne-Tethered Biaryls进行非对称的增氧化功能化
1Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry and Sichuan Province, and Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, Chengdu 610041, China.
Organic letters
|September 17, 2025
概括
研究人员开发了一种新的非对称的 dearomatization 反应用于 biaryls 使用和奇拉酸. 这种方法有效地产生具有高反选择性的复杂螺旋环化合物,提供了一种新的合成途径.
科学领域:
- 有机化学 有机化学
- 不对称的催化剂.
- 合成方法论 合成方法论
背景情况:
- 双化合物是药品和材料中重要的结构图案.
- 开发用于复杂分子不对称合成的高效方法是一个关键的挑战.
- Dearomatization 反应提供了一个强大的策略来构建复杂的分子架构.
研究的目的:
- 为 enyne-tethered biaryls 开发一种新型不对称的 dearomatization 反应.
- 在合成螺旋环六和印度林因的过程中实现高的反选择性.
- 阐明了涉及和酸的催化机制.
主要方法:
- 采用(0) 催化剂与酸联合使用.
- 利用enyne-tethered biaryls的分子内功能化.使用enyne-tethered biaryls的分子内功能化.
- 研究反应条件以优化产量和酶选择性.
主要成果:
- 成功实现了对enyne-tethered biaryls的不对称的 dearomatization. 这是一个很好的例子.
- 螺旋环六和印林被合成,具有相当优异的反选择性.
- 一个拟议的机制涉及Pd(0) π-易斯基促进的质子与的酸盐离子介导enantiocontrol.
结论:
- 开发的方法提供了一条高效的途径,以致于以酶体丰富的螺旋环化合物.
- 和奇拉酸的组合对于反应的成功和立体控制至关重要.
- 这项工作扩大了不对称的 dearomatization 反应的范围,并提供了有价值的合成工具.
相关概念视频
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.8K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
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...
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...
3.8K
02:34Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
9.5K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
9.5K
02:36Regioselectivity and Stereochemistry of Hydroboration
9.4K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
9.4K
01:15α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
3.7K
The method to achieve α-brominated carboxylic acids using a mixture of phosphorus tribromide and bromine is known as the Hell–Volhard–Zelinski reaction. The reaction is catalyzed by phosphorus tribromide, which can be used directly or produced in situ from red phosphorus and bromine. The mechanism comprises PBr3 catalyzed conversion of acid to acid bromide and hydrogen bromide. The acid bromide enolizes to its enol form in the presence of HBr. The nucleophilic enol attacks the...
3.7K
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
20.7K
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.
20.7K
01:25Radical Anti-Markovnikov Addition to Alkenes: Overview
4.0K
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
4.0K