催化不对称转移β,γ-不和α-Diketones的化
Zhifei Zhao1, Wennan Dong1, Jinggong Liu2
1State Key Laboratory of Structural Chemistry, 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
|November 27, 2024
概括
这项研究引入了一种新的非对称转移化 (ATH) 协议,用于β,γ-不和α-二基,产生和1,2-二醇. 这一突破为药物发现和合成提供了有效的合基石.
科学领域:
- 有机化学
- 不对称的催化
背景情况:
- 非对称转移化 (ATH) 对于合成丰富化合物至关重要,特别是在药品制造中.
- 有效和有选择的ATH方法对enones和获取奇拉性acyloins/1,2-diols仍然具有挑战性.
研究的目的:
- 为β,γ-不和α-二基开发一种高效的非对称转移化 (ATH) 协议.
- 提供简洁的不对称的各种酸和光学纯净的1,2-二醇.
主要方法:
- 随时可用的β,γ-不和α-二基的不对称转移化 (ATH).
- 系统的机械研究和密度函数理论 (DFT) 的计算.
主要成果:
- 该协议在β,γ-不和α-二基上实现了高效,区域和立体选择性ATH.
- 它提供了四种酸和四种光学纯净的1,2-二醇.
- 通过四种自然产品的合成合成证明了合成效用.
结论:
- 这项工作介绍了第一个高效的β,γ-不和α-二基的ATH,扩大了不对称合成的范围.
- 机理研究为ATH的基质依赖反应性和替代剂效应提供了独特的见解.
- 开发的方法为有机合成和药物化学提供了有价值的合基石.
相关概念视频
Reduction 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
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
3.6K
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...
3.6K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.6K
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.
7.6K
Reduction of Alkenes: Catalytic Hydrogenation
11.8K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
11.8K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
17.8K
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.
17.8K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
9.8K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
9.8K


