通过化/异构化级联,Ru催化α,β不和子的不对称化
Kun Wang1,2, Saisai Niu2, Weijun Tang2
1Huzhou Key Laboratory of Green Energy Materials and Battery Cascade Utilization, School of Intelligent Manufacturing, Huzhou College, Huzhou, 313000, China.
催化不对称化使得从不和子中高效合成性酒精. 这种方法通过一种涉及异构化和动态运动分辨率的新机制实现了高立体选择性.
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:
- 基拉尔α替代二次醇是制药和精细化学品中宝贵的构建模块.
- 开发高效和选择性的合成方法仍然是有机化学的一个重大挑战.
研究的目的:
- 开发一种新的鲁丁催化非对称化方法,用于性α替代二次醇的酶选择性合成.
- 阐明反应机制并确定控制立体选择性的关键因素.
主要方法:
- 使用催化剂对α替代的α,β不和子进行不对称的化.
- 机械学研究,包括乳标记和中间分析.
- 反应条件的优化以最大限度地提高二重选择性 (dr) 和反选择性 (ee).
主要成果:
- 实现了性α替代二次醇的高度对抗选择性合成.
- 证明了出色的二聚体选择性 (高达>99:1 dr) 和对抗选择性 (高达98% ee).
- 提出了一种涉及Ru催化C=O化和基促进基醇异构化的机制,其中立体化学由动态动态分辨率 (DKR) 控制.
结论:
- 开发的Ru-催化不对称化是一种强大的方法,可以获得性α-替代的二次醇.
- 反应通过一种独特的途径进行,结合化,异构化和DKR.
- 这种方法在合成基纯酒精方面取得了重大进展.
更多相关视频
12:08Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes
Published on: June 24, 2022
05:34Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes
Published on: December 16, 2019
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
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...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
Reduction of Alkenes: 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...
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
