相关实验视频
Updated: May 23, 2026

09:45
A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
二级和三级有机的内部分子化
Julien Lefranc1, Anne M Fournier, Gaëlle Mingat
1School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Journal of the American Chemical Society
|April 7, 2012
概括
来自尿素,碳酸盐和硫酸盐的基碳酸盐以分子内方式迁移基基团. 这种反应产生了具有新立体中心的有价值的基胺,在有机合成中很有用.
科学领域:
- 有机化学 有机化学
- 立体选择性合成 立体选择性合成
背景情况:
- 基炭基离子是有机合成中的多功能中间体.
- 内部分子重组为复杂分子提供了高效的路线.
研究的目的:
- 研究来自尿素,碳酸盐和硫酸盐的基碳酸的分子内基基团迁移.
- 探索这种重新排列的立体化学结果和合成实用性,以产生基丰富产品.
主要方法:
- 脱化N'-基基替代基尿素,碳酸盐和硫酸盐.
- 由此产生的尿素产品的溶解.
- 对产品进行立体化学分析.
- 计算和现场红外 (IR) 光谱学研究.
主要成果:
- 从这些基质产生的碳离子容易经历基基团的分子内迁移.
- 尿素产品的溶解产生α-基胺胺.
- 基纯净的起始材料以基丰富的形式产生基氨基胺与N载基基四级立体基中心.
- 反应通过协调的添加-消除途径进行.
结论:
- 这项研究证明了一种新的立体特异性重组,用于合成基丰富的α-基氨基胺.
- 这种方法可以获取含有基四分制立体中心的有价值的构建块.
- 这些发现提供了对这种重要的有机转化机制的见解.
相关概念视频
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 Halides to Alcohols: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert acid halides to tertiary alcohols. The reaction requires two equivalents of the Grignard reagent and proceeds via a ketone intermediate.
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Preparation of Alcohols via Substitution Reactions
Overview
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
α-Alkylation of Ketones via Enolate Ions
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 strong interaction...
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
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...
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...

