铜催化基与二利盐的结合
Robert J Phipps1, Lindsay McMurray, Stefanie Ritter
1Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Journal of the American Chemical Society
|June 21, 2012
概括
一种新的铜催化方法使得使用diaryliodonium盐进行基化,与Heck反应相比,提供了不同的产物. 这种方法促进了复杂分子合成的新联体和级联反应.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成化学 合成化学
背景情况:
- 基和基是有机合成中的基本构建块.
- 像赫克反应这样的传统方法对烯合的产品多样性有局限性.
研究的目的:
- 开发一种使用diaryliodonium盐的基化新方法.
- 基于这种结合方法,探索新的并列和级联反应.
主要方法:
- 使用diaryliodonium盐作为化剂.
- 采用铜 (Cu) 催化剂用于化反应.
- 研究了与各种简单基因的反应.
主要成果:
- 取得了成功的基与diaryliodonium盐的化.
- 与赫克反应相比,观察到明显不同的产品结果.
- 开发了新的联反应和级联反应,用于合成复杂的联产物.
结论:
- 开发的Cu-催化方法为基化提供了一条新的途径.
- 这种方法扩大了合成的可能性,超出了传统的赫克反应.
- 新的双重和级联反应在化学合成中提供了广泛的应用.
相关概念视频
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
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 Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.


