(ヘテロ) アリル金属の非デプロトン性一次および二次アミネーション
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PubMedで要約を見る
まとめ
この要約は機械生成です。新しい方法は,銅の触媒を用いてアリルおよびヘテロアリル化合物へのアミノ群の容易な転送を可能にします. この効率的なプロセスは低温で動作し,様々な機能群を許容します.
科学分野
- 有機化学
- 有機金属化学
- カタリシス
背景
- アミネーション反応は窒素を含む化合物の合成に不可欠である.
- 伝統的な方法はしばしば貴金属触媒,リガンド,および保護グループを必要とし,その範囲と効率を制限します.
- 触媒性,無金属,または低金属負荷のアミネーションの方法の開発は非常に望ましい.
研究 の 目的
- アリルとヘテロアリルクパレットのアミネーションのための新しい,簡単で広く適用可能な方法を開発する.
- 高価な金属の触媒や複雑な反応条件に頼らずに低温でアミネーションを達成する.
- 機能群の許容性と開発されたアミネーション方法の範囲を証明する.
主な方法
- アミノ群の移転のための新しい銅 ((I)) 触媒法を使用する.
- 主要な (-NH2) と二次的なアミノ群 (-NHR) を核愛体として使用する.
- アリルとヘテロアリルカップレートと軽度な低温条件で反応する.
- 変換は"ポット"で実行する.
主要な成果
- 主要および二次アミノ基をアリルおよびヘテロアリルカップレートに簡単に転送する.
- 反応は低温で効率的に進行する.
- この方法は,電子が豊富で,電子が不足し,構造的に複雑な (ヘテロ) アリル金属を含む幅広い機能群の許容性を示しています.
- いくつかのケースでは,銅 ((I) 塩の触媒量のみが求められ,貴金属触媒,リガンド,または保護グループを必要としない.
結論
- (ヘテロ) アリル金属をアミネーションするための新しい効率的な方法が開発されました.
- この方法は,単純さ,機能群の耐性,軽度の反応条件という点で大きな利点があります.
- このアプローチは,多様なアリルとヘテロアリルアミンの合成のための貴重なツールを提供します.
関連する概念動画
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...
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...
Alkylation is one of the methods used to prepare amines. Direct alkylation of ammonia or a primary amine with an alkyl halide gives polyalkylated amines along with a quaternary ammonium salt through successive SN2 reactions. This process of making the quaternary salt through the direct alkylation method is called exhaustive alkylation.
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...
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...
Nitriles can be reduced to primary amines using reducing agents like lithium aluminum hydride or catalytic hydrogenation. The reduction introduces an amino group with an extra carbon in the skeleton. Nitriles are formed from the reaction between alkyl halides and sodium cyanide through the SN2 mechanism. Primary alkyl halides are the preferred substrates to prepare nitriles.
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...
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.
Reductive amination using sodium cyanoborohydride as the reducing agent is called the Borch reaction. Sodium cyanoborohydride is a mild...