O-H 连接促进了从α C-H 连接中转移 H 原子以进行酒精的C-化
Jenna L Jeffrey1, Jack A Terrett1, David W C MacMillan2
1Merck Center for Catalysis, Princeton University, Princeton, NJ 08544, USA.
这项研究详细介绍了一种使用光反氧催化和原子转移进行选择性化的新催化方法. 酸增强了特定的酒精C-H键的选择性.
科学领域:
- 有机化学
- 光催化
- 反应机制
背景情况:
- 由于多个反应点,控制有机分子中的原子转移选择性具有挑战性.
- 选择性功能化酒精对于合成复杂的有机分子至关重要.
研究的目的:
- 在机理上评估一种用于选择性α-alkylation/lactonization的新型光反催化系统.
- 研究添加剂在增强原子转移反应的作用.
主要方法:
- 涉及光催化物的机制研究.
- 用甲基酸盐对酒精的选择性α-化/乳酸化进行评估.
- 测定酸对反应选择性的影响.
主要成果:
- 开发了一种高度选择性的光反氧催化方法,用于α-化/乳酸化酒精.
- 证明四甲基酸盐显著提高了酒精中α-C-H键的选择性.
- 确定了从α-C-H键转移到基,基,α-C=O和α-基C-H键的优先转移.
结论:
- 描述的催化系统为选择性酒精功能化提供了强大的策略.
- 酸在指导原子转移到特定的酒精C-H键中起着关键作用.
- 这项工作为选择性光氧化催化提供了有价值的机制见解.
更多相关视频
06:46Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
06:34Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS
Published on: June 20, 2014
相关概念视频
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...
Aldehydes and Ketones with Alcohols: Hemiacetal Formation
Preparation of Alcohols via Addition Reactions
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
Hydroboration-Oxidation of Alkenes
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.
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...
