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

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.

非光气合成N-取代氨基甲酸酯的研究进展

简述了近年来国内外非光气合成N-取代氨基甲酸酯的主要方法,重点阐述了以CO、碳酸二甲酯、CO2、氨基甲酸烷基酯等为羰基化试剂的合成途径,并对各合成方法的优缺点进行了系统的评述。指出氨基甲酸烷基酯以其毒性低、活性高以及制备简单等优点使其成为合成N-取代氨基甲酸酯最具工业化应用前景的羰基化试剂;而以CO2为羰基化试剂合成N-取代氨基甲酸酯的路线符合当前绿色化学的主题,为CO2的资源化利用提供了新途径,是今后的研究热点。

1,6-己二氨基甲酸酯合成的研究进展

综述了1,6-己二氨基甲酸酯(HDC)合成所用的羰基化试剂及其相关的各类催化剂。对CO、CO2、碳酸二甲酯(DMC)和氨基甲酸酯等羰基化试剂合成HDC的优缺点进行了系统评述。指出氨基甲酸酯的低毒、高活性、来源广等优点使其发展为合成HDC最具工业化前景的羰基化试剂;同时对碳酸二甲酯和氨基甲酸酯制备HDC的催化剂进行了介绍、分类、评述和总结,以期为开发高效HDC合成催化剂提供指导。最后表明制备廉价、易分离回收和循环利用的环境友好催化剂是推动HDC产业化的关键。