用铜催化三甲基化终端基因通过基C-H键激活
1Department of Chemistry, Joint Laboratory of Green Synthetic Chemistry, University of Science and Technology of China, Hefei 230026, China.
Journal of the American Chemical Society
|September 15, 2011
概括
铜催化使终端基因通过C ((sp ((3)) -H激活实现了新的三甲基化. 这种反应提供了一个独特的机制,涉及基C-H功能化和Heck-like过渡状态.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 有机金属化学 有机金属化学
背景情况:
- 三甲基化对于改变分子性质至关重要.
- 催化C-H激活提供了高效的合成路径.
- 铜催化反应在现代合成中至关重要.
研究的目的:
- 报告一个新的铜催化三甲基化终端基.
- 通过C(sp(3)) -H激活来证明三甲基化.
- 为了阐明反应机制.
主要方法:
- 铜催化反应的优化.
- 实验机理学研究.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 实现了前所未有的Cu-催化三甲基化终端基.
- 反应通过催化C(sp(3)) -H激活进行.
- 实验和理论数据表明,一个Heck-like四个成员的环过渡状态.
结论:
- 这项研究引入了使用铜催化剂进行三甲基化的一种新方法.
- 反应机制涉及一个独特的基C-H激活通路.
- 这些发现为C-H功能化策略提供了洞察力.
相关概念视频
Radical Substitution: Allylic Bromination
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
Radical Substitution: Allylic Chlorination
Typically, when alkenes react with halogens at low temperatures, an addition reaction occurs. However, upon increasing the temperature or under reaction conditions that form radicals, providing a low but steady concentration of halogen radicals, allylic substitution reaction is favored. This is because allylic hydrogens are very reactive as the formed intermediate is resonance stabilized. For example, when propene is treated with chlorine in the gas phase at 400 °C, it undergoes allylic...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
Base-Promoted α-Halogenation of Aldehydes and Ketones
α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base. The reaction begins with the abstraction of α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction at the stage of...
Electrophilic Addition to Alkynes: Hydrohalogenation
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
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...


