C ((sp3) -H アモニア由来銅のアミドによるアミネーション
Maxwell S Reese1, Joshua A Queener1, Curtis E Moore1
1Department of Chemistry & Biochemistry, The Ohio State University, 100 W 18th Avenue, Columbus, Ohio 43210, United States.
Journal of the American Chemical Society
|August 4, 2025
まとめ
研究者はアンモニア (NH3) とアミド (NH2) リガンドで銅複合体を合成した. 彼らは,C-H結合をC-NH2結合に変換することを可能にする,金属-アミン複合体の中で最も強いN-H結合を達成した.
科学分野:
- 無機化学
- 有機金属化学
- カタリシス
背景:
- メタルアミンとメタルアミドは,アンモニアの酸化における重要な中間物質である.
- これらの複合体の弱いN-H結合は,通常,連続的な結合破裂を容易にする.
- 金属-アミン複合体における高いN-H結合解離自由エネルギー (BDFE) は珍しいが,特定の合成用途には望ましい.
研究 の 目的:
- アンモニア (NH3) とアミド (NH2) リガンドによる新しい銅 (II) と銅 (III) コンプレクスを合成し,特徴づけること.
- 銅 (II) アミン複合体のN−H結合強さを調べる.
- 銅 (III) アミド複合体のC (sp3) -H機能化の反応性を探求する.
主な方法:
- 銅-アミンおよび銅-アミド複合体の合成と特徴付け.
- N-H結合解離自由エネルギー (BDFE) を実験手法で測定する.
- C ((sp3) -H機能化反応における触媒活性の評価
主要な成果:
- 銅(II) アミン複合体 (LCuII NH3) は,M-NH3種で報告された最高N-H BDFEを92.8(1.5) kcal/molで示した.
- 公式の銅 (III) アミド共生体 (LCuIII NH2) は,C (sp3) -H結合に対する反応性を示した.
- C ((sp3) -H活性化とC ((sp3) -N結合形成の効率的なメディエーションが達成され,ニトリル,ケトン,および一次アミンが得られた.
結論:
- 銅とアミンの複合体では前例のないほど強いN-H結合が報告されています.
- 銅 (III) アミド複合体は,C (sp3) -H機能化の効果的な触媒として機能する.
- これらの発見は,C−N結合形成を通じて機能化された炭化水素を合成するための新しい道を開く.
関連する概念動画
Preparation of 1° Amines: Gabriel Synthesis
3.8K
Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred method to exclusively make primary amines. The method uses phthalimide, which contains a protected form of nitrogen that participates in alkylation only once to predominantly give primary amines.
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
3.8K
Preparation of 1° Amines: Azide Synthesis
4.1K
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
4.1K
Acid Halides to Amides: Aminolysis
3.1K
Aminolysis is a nucleophilic acyl substitution reaction, where ammonia or amines act as nucleophiles to give the substitution product. Acid halides react with ammonia, primary amines, and secondary amines to yield primary, secondary, and tertiary amides, respectively.
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
3.1K
Preparation of Amides
3.2K
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...
3.2K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
3.6K
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...
3.6K
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
3.1K
Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.
3.1K


![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)