羧胺与胺的转酰胺反应——基于异烟碱腙的钌（II）配合物催化的分子内CN裂解/CN偶联反应

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2025-09-27 DOI:10.1016/j.ica.2025.122936

Jayapratha Gunasekaran , Gowtham Sekar , Denzil Britto Christopher Leslee , Narmatha Venkatesan , Luis G. Alves , Ana M. Martins , Shanmuga Bharathi Kuppannan

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引用次数: 0

摘要

合成了一系列半夹心[Ru（η - 6-对伞花烃）（Cl）（异烟碱腙）]配合物，并用FT-IR、UV-Vis、NMR和ESI-MS对其进行了表征。单晶x射线衍射测定的[Ru（η - 6-p-花蔷薇烯）（Cl）(L)] （L = N′-（萘-5-基亚甲基）异烟酰肼）的固态分子结构显示出围绕金属中心的三腿钢琴凳几何结构。研究了Ru（II）配合物家族在伯胺与伯胺催化转酰胺生成仲酰胺过程中的催化活性。催化机制涉及转酰胺，可能通过分子内环化和CN键裂解形成仲酰胺。在温和的反应条件下，对各种底物进行了测试，显示出良好的收率（75 - 96%）。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Transamidation of carboxamides with amines – An intramolecular CN cleavage/CN coupling reaction catalyzed by Ruthenium(II) complexes based on isonicotinichydrazones

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Transamidation of carboxamides with amines – An intramolecular CN cleavage/CN coupling reaction catalyzed by Ruthenium(II) complexes based on isonicotinichydrazones

A series of half-sandwich [Ru(η⁶-p-cymene)(Cl)(isonicotinichydrazone)] complexes were synthesized and fully characterized by FT-IR, UV–Vis, NMR and ESI-MS spectroscopy. The solid-state molecular structure of [Ru(η⁶-p-cymene)(Cl)(L)] (L = N′-((naphthalen-5-yl)methylene)isonicotinohydrazide) determined by single-crystal X-ray diffraction shows a three-legged piano-stool geometry around the metal center. The catalytic activity of this new family of Ru(II) complexes was also studied in the catalytic transamidation of primary amides with primary amines to form secondary amides. The catalytic mechanism involves transamidation that likely occurs through intramolecular annulation and CN bond cleavage to form secondary amides. A variety of substrates have been tested showing good to excellent yields (75–96 %) under mild reaction conditions.

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.