相关实验视频
Updated: Jul 9, 2025
![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
05:15
Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
6.9K
通过固相合成为1,4,7-Triazacyclononane配备替代剂
Daniel Ossadnik1, Jona Voss1, Adelheid Godt1
1Faculty of Chemistry and Center for Molecular Materials (CM2), Bielefeld University, Universitätsstraße 25, 33615 Bielefeld, Germany.
The Journal of organic chemistry
|November 28, 2023
概括
研究人员开发了一种固相合成策略,用于创建多种替代的1,4,7-triazacyclononane (tacn) 配体. 这种方法可以制备复杂的金属离子协调球体,其电子和功能性能为各种应用量身定制.
科学领域:
- 协调化学 协调化学
- 有机合成 有机合成
- 材料科学 材料科学 材料科学
背景情况:
- 替代的1,4,7-triazacyclononane (tacn) 连接体在金属离子复杂化学中至关重要.
- 技术支架允许功能化调整金属离子特性,并添加像吸光天线或生物结合组这样的功能.
- 需要对非对称替代的TACN配体 (NO,R1,R1,R2和NO,R1,R2,R3) 进行定向合成,以充分利用它们的潜力.
研究的目的:
- 开发一种策略,用于非对称替代的TACN配体的定向合成.
- 为了使两种和三种不同的替代剂 (R) 能够制备tacn衍生物.
- 为了证明开发的合成策略的广泛适用性.
主要方法:
- 固体相合成方法使用 (4-尼托二碳酸盐) -树脂.
- 在树脂上加载tacn以形成树脂结合的 (rb) -tacn (NO(Cbz,H,H)).
- 选择性功能化rb-tacn与乙烯三乙酸以产生rb-NO(tfAc,H) (NO(Cbz,tfAc,H)).
- 随后在树脂结合的中间体上进行多种反应,以引入各种替代物 (R1,R2,R3).
主要成果:
- 建立了一个强大的固体相合成策略,用于组装NO(R1,R1,H) 和NO(R1,R2,H) 前体.
- 该方法在形成NO,Cbz,tfAc,H等关键中间体方面表现出高的选择性.
- 通过核替代,还原性氨化,阿扎-迈克尔添加,环氧开放和化反应,成功引入了广泛的替代剂.
- 该研究确定了合成策略的局限性和未来改进的领域.
结论:
- 开发的固体相合成策略提供了对多种多样替代的TACN配体的有效访问.
- 这种方法有助于创建具有定制功能的复杂金属离子协调球.
- 该方法对推进各种应用新型金属复合物的设计具有前景.
相关概念视频
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
1.9K
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...
1.9K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
3.2K
In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.
3.2K
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
2.1K
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,...
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
2.1K
Preparation of Alkynes: Alkylation Reaction
10.2K
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.
10.2K
Diazonium Group Substitution: –OH and –H
2.8K
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
2.8K
Preparation of Amides
3.0K
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
3.0K

