Controlling Reactivity of Palladium Amides for Selective Carbonylation towards Urea and Oxamide Derivatives  

由钯酰胺反应性调控胺的单羰和双羰化反应合成脲和草酰胺衍生物

作　　者：WANG Jin-hui CAO Yan-wei HE Lin 锦辉;曹彦伟;何林(中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,甘肃兰州730000;中国科学院大学,北京100049)

机构地区：[1]State Key Laboratory for Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China [2]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《分子催化（中英文）》2024年第4期297-308,共12页Journal of Molecular Catalysis(China)

基　　金：The National Key Research and Development Program of Ministry of Science and Technology(No.2022YFA1504602);Natural Science Foundation of Jiangsu Province(No.BK20211094);National Natural Science Foundation of China(No.22302214,21972152,U22B20137).

摘　　要：Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways.Herein,our study introduces a strategy employing palladium amides,harnessing their unique reactivity control,to direct the selective carbonylation of amines for the targeted synthesis of urea and oxamide derivatives.The palladium amide structure was elucidated using single-crystal X-ray diffraction.Controlled experiments and cyclic voltammetry studies further elucidate that the oxidation of palladium amide or its insertion into a carbonyl group diverges into distinct pathways.By employing sodium percarbonate as an eco-friendly oxidant and base,we have successfully constructed a switchable carbonylation system co-catalyzed by palladium and iodide under room temperature.The utilizing strategy in this study not only facilitates effective control over reaction selectivity but also mitigates the risk of explosions,a critical safety concern in traditional carbonylation methods.羰基化反应可以在分子中引入羰基,然而,在同种底物上实现精确的选择性单或双羰基化仍是一项挑战.因此,我们提出了一种新策略,通过精准控制钯酰胺的反应性来合成脲和草酰胺衍生物.通过单晶X射线衍射,我们详细揭示了钯酰胺的结构.进一步的控制实验和循环伏安法研究帮助我们深入理解了钯酰胺在羰基化反应中,通过氧化或插入羰基实现单羰基化或双羰基化的具体机制.通过使用环保的过碳酸钠作为氧化剂和碱,在常温条件下,我们成功开发了一种由钯和碘共催化的可控羰基化体系.该策略不仅显著提高了反应选择性,同时也降低了传统羰基化方法可能带来的爆炸风险,为实验室安全提供了额外的保障.

关 键 词：selectivity control palladium catalysis oxidative carbonylation AMINOCARBONYLATION green reagents 

分 类 号：O643.32[理学—物理化学]