通过不对称转移化对β-替代α-二基的动态动态分辨率
Ting Chen1, Wenjun Liu1, Wei Gu2
1State Key Laboratory of Structural Chemistry, and Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.
Journal of the American Chemical Society
|December 23, 2022
概括
这项研究引入了一种新的动态动态分辨率 (DKR) 方法,用于非对称α-二基的非对称半化. 这一过程产生了酸,对合成药物分子有价值.
科学领域:
- 有机化学
- 不对称的催化
- 绿色化学
背景情况:
- 在非对称α-二基的半化中实现高的区域和反抗选择性仍然是一个重大挑战.
- 开发创新的动态动态分辨率 (DKR) 策略对于推进非对称 (转移) 化至关重要.
研究的目的:
- 为非对称α-二基的高度区域和立体选择性的非对称半转移化开发一种新的DKR模式.
- 合成一种具有α-基-α'-C(sp2) 功能群的基.
主要方法:
- 使用一个独特的DKR模式, 准碳基离位到的立体中心.
- 使用不对称的转移化,重点是选择性碳缩.
- 进行密度函数理论计算和控制实验以阐明机制.
主要成果:
- 在非对称α-二基的半化中获得高的区域和立体选择性.
- 已经成功合成了一种新型的酸.
- 证明了产品在合成药物分子中的有用性.
结论:
- 开发的DKR模式为选择性合成有价值的丰富提供了强大的策略.
- 该协议提供了一个新的产品类别, 在药物合成中已经证明了其应用.
- 通过计算和实验研究获得了机械洞察力,为不对称化进一步进步铺平了道路.
更多相关视频
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.4K
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...
3.4K
α-Alkylation of Ketones via Enolate Ions
3.3K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
3.3K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.6K
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.
18.6K
Aldol Condensation with β-Diesters: Knoevenagel Condensation
3.1K
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.
3.1K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
4.0K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
4.0K
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
3.5K
Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an...
3.5K


