摘要/Abstract
异腈是一种含有稳定二价碳原子的重要活性反应物,在含氮化合物的构建、新药物的研发以及天然产物的合成中得到了广泛的应用.在过去的十年中,以Passerini和Ugi反应为基础,化学家们致力于研究异腈参与的多组分反应.最近,过渡金属催化异腈参与的氧化偶联反应得到广泛的发展,而使用的催化剂主要集中在一些贵重的过渡金属(Pd、Rh、Ag等)化合物,如何利用廉价过渡金属Co来催化异腈参与的偶联反应具有非常重要的意义.在这里我们概述了近年来Co催化异腈参与的偶联反应的最新研究进展.
关键词: 异腈, 含氮化合物, 钴催化, 偶联反应, 自由基反应
Isocyanide is an important reactive reactant containing stable divalent carbon atoms, which has been widely used in the construction of nitrogen compounds, new drugs and natural products. During the past decades, exhaustive efforts have been devoted to the discovery of highly efficient reactions involving isocyanide on the basis of the development of the Passerini and Ugi reactions. Several types of reactions involving isocyanides have been reported, such as nucleophilic attack, electrophilic addition, imidoylation reactions, and oxidation, etc. Recently, isocyanides have found a new application as versatile C1 building blocks in transition metal catalysis. The transition metal catalyzed reactions involving isocyanide insertion offer a vast potential to construct C—C or C-N bonds for the synthesis of nitrogen-containing fine chemicals. As we know, the catalysts used in isocyanide insertion reactions are mainly concentrated in some valuable transition metals compounds, such as Pd, Rh, Ag and other metals. Therefore, the development of catalysts based on the naturally more abundant, cost efficient transition metal complexes, represents an attractive alternative. In this context, rather environmentally benign cobalt complexes bear great potential for applications in the coupling reactions. The reduced electronegativity of cobalt as compared to the homologous group 9 elements translates into more nucleophilic organometallic cobalt intermediates which allow for unprecedented reaction pathways in transition-metal catalyzed C—H activations as well as significantly improved positional and chemo-selectivities. And in the recent years, notable success has been achieved with the development of cobalt catalyzed C—H functionalizations with either in situ generated or single-component cobalt-complexes under mild reaction conditions. How to find and use the cost efficient cobalt-complexes to catalyze the isocyanide coupling reaction is of great significance. Our group has been devoted to explore the isocyanide chemistry, and in recent years, we have achieved several progresses in the reaction of cobalt-catalyzed isocyanides. In this review we summarize the recent advances in the cobalt-catalyzed isocyanide coupling reactions.
Key words: isocyanide, nitrogen-containing chemicals, Co-catalysis, coupling reaction, free radical reaction
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