合成,表征和功能化 κ1N amidinato复合物从碳二化物
Marcel Eilers1, Saskia Bültena1, Kevin Schwitalla1
1Institut für Chemie, Carl von Ossietzky Universität Oldenburg, D-26111 Oldenburg, Germany. ruediger.beckhaus@uol.de.
Dalton transactions (Cambridge, England : 2003)
|December 13, 2024
概括
胺酸复合物是通过将碳二胺插入到-的前体中来合成的. 这种反应提供了逐步的功能化,并揭示了复合物的新反应途径.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 合成化学 合成化学
背景情况:
- 复合物与环丁类型连接体是多功能合成平台.
- 碳二胺是有机和有机金属合成中的有价值的构建模块.
- 了解连接体插入反应对于开发新型催化系统至关重要.
研究的目的:
- 为了合成新的胺酸复合物.
- 为了研究碳二胺插入反应的机制和范围,进入-pentafulvene复合体.
- 为了探索由此产生的功能化复合物的反应性.
主要方法:
- 碳二胺的固体测量插入反应.
- 合成 bis ((π-η5:σ-η1-pentafulvene) 复合物. 这种复合物在中具有非常大的作用.
- 核磁共振 (NMR) 光谱学.核磁共振 (NMR) 光谱学.
- 单晶X射线衍射. 单晶X射线衍射.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 通过碳胺插入成功合成了胺化合物复合物.
- 对中心的碳二胺基的 κ1N 协调的演示.
- DFT的计算证实了对单牙协调的偏好,以及对化联结体形成的高过渡状态.
- 实现了碳二胺的逐步插入到Ti-C键中,这取决于pentafulvene连接体.
- 通过与H酸和多重键基质的反应,观察到复合物的进一步功能化.
结论:
- 这项研究确立了易于获得胺酸复合物的途径.
- 这些发现突出了复合物的受控,逐步的功能化.
- 在这些系统中,pentafulvene连接体的反应性得到了进一步阐明,为各种应用打开了道路.
相关概念视频
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
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
4.4K
Primary amines react with carbonyl compounds—aldehydes and ketones—to generate imines. Imines consist of a C=N double bond and are named Schiff bases after its discoverer—the German chemist Hugo Schiff. On the other hand, secondary amines react with carbonyl compounds to give enamines. In enamines, the presence of a C=C double bond adjacent to the nitrogen atom leads to the delocalization of the lone pair.
4.4K
Aldehydes and Ketones with Amines: Imine Formation Mechanism
5.3K
Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
5.3K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
3.4K
The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...
3.4K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
3.7K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
3.7K


