在化控制的过程中,对α-chloro aldimines添加有机
Gretchen R Stanton1, Per-Ola Norrby, Patrick J Carroll
1Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
Journal of the American Chemical Society
|September 26, 2012
概括
这项研究揭示了碳化合物键如何控制化学反应中的立体化学. 基化物与基质协调,通过化控制实现高度二聚选择性碳-碳键的形成.
科学领域:
- 有机化学 有机化学
- 立体化学是一种立体化学.
- 有机金属化学 有机金属化学
背景情况:
- 对α-碳酸化合物的核性添加通常通过非化途径产生Cornforth-Evans产物.
- 在C-C键形成中的二重选择性对于合成复杂分子至关重要.
研究的目的:
- 调查C-X键在金属介导的C-C键形成过程中逆转立体选择性的前所未有的作用.
- 为了证明合控制涉及C-X键在有机添加到α-chloroaldimines.
主要方法:
- 将有机试剂添加到α-chloro-aldimine基质中.
- 使用基化物易斯酸用于金属协调.
- 运用计算研究来支持机械学假设.
主要成果:
- 已证明对α-chloro-aldimines的有机试剂的高度二重选择性添加.
- 展示了通过C-X键介导的化控制,扭转了典型的立体化学结果.
- 识别了化基化的易斯酸,与基质的Cl,N和O原子协调.
结论:
- C-X 键可以通过金属协调 (化控制) 积极参与控制立体化学.
- 这种机制为在C-C键形成反应中实现高立体选择性提供了一个新的策略.
- 这些发现扩大了对有机合成中的立体化学控制的理解.
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.
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation of Alkenes
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Conjugate Addition to α,β-Unsaturated Carbonyl Compounds
α,β-Unsaturated carbonyl compounds are molecules bearing a carbonyl and alkene functionality in conjugation with each other. The conjugation in the molecule leads to three resonance structures. The hybrid form exhibits two probable electrophilic sites: the carbonyl carbon and the β carbon.
Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition)
α,β-Unsaturated carbonyl compounds with two electrophilic sites, the carbonyl carbon, and the β carbon, are susceptible to nucleophilic attack via two modes: conjugate or 1,4-addition and direct or 1,2-addition.
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are formed faster owing to...
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are formed faster owing to...
α-Halogenation of Carboxylic Acid Derivatives: Overview
Unlike aldehydes and ketones, carboxylic acids do not readily participate in α halogenation reactions via enols or enolate intermediates. However, α-halogenated acids are obtained through other methods. One of the approaches is the Hell–Volhard–Zelinsky (HVZ) reaction, wherein the carboxylic acid is treated with halogen in the presence of PBr3. It involves the conversion of acid to acid halide, which exists in equilibrium with its enol form. The enol attacks the electrophilic halogen to produce...


