简单的化物和胺的催化动态动态减少性添加与 heterobiaryl triflates:利用中央和轴向性
Hui Ni1, Anyao Liu1, Xiaoying Fu1
1State Key Laboratory of Natural Medicines (SKLNM) and Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 211198, China. yulihe@cpu.edu.cn.
Organic & biomolecular chemistry
|May 23, 2025
概括
这项研究介绍了一种催化方法,用于从racemic起始材料中创建奇拉分子. 该过程实现了轴性性高选择性,产生了用于催化的有价值化合物.
科学领域:
- 有机化学 有机化学
- 不对称的合成方法
- 催化剂是一种催化剂.
背景情况:
- 轴性性异构是不对称合成中的关键组成部分.
- 合成基纯净的轴性性化合物往往会带来重大挑战.
- 动态动态分辨率 (DKR) 为克服这些合成障碍提供了一个潜在的战略.
研究的目的:
- 开发一种高效的催化分子内 DKR 策略,用于合成 enantioselective 轴性性 heterobiaryl.
- 为了同时控制轴向和中心度.
- 探索合成的性异构在不对称转换中的实用性.
主要方法:
- 使用催化分子内动态动力学分辨率 (DKR) 方法.
- 作为起始材料使用的racemicazabiaryltriflates.
- 研究了用于立体化学控制的还原性加法机制.
主要成果:
- 实现了带有广泛基质范围的轴性奇拉性异构的酶选择性合成.
- 证明了出色的 enantioselectivity 和环球选择性.
- 在不对称反应中成功利用合成的性异构作为有机催化剂和性配体.
- 机械研究表明,动力分辨率和介导的立体化学反转之间存在协同作用.
结论:
- 开发的催化DKR策略提供了一条有效的途径,以致于对抗聚合物丰富的轴性性异构.
- 该方法解决了对轴向和立体化学配置的并发控制的挑战.
- 合成的性异构呈现出显著的潜力,作为多功能工具在不对称催化.
相关概念视频
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.2K
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...
3.2K
01:25Radical Anti-Markovnikov Addition to Alkenes: Overview
3.3K
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
3.3K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
17.9K
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.
17.9K
02:36Regioselectivity and Stereochemistry of Hydroboration
8.1K
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...
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...
8.1K
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.7K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
7.7K