碳氢键活化一氧化碳羰基化偶联反应研究进展

A review on transition-metal catalyzed C–H bond carbonylation reactions with CO

自从Heck小组于1974年报道了有机卤代物的插一氧化碳(CO)反应之后,羰基化反应便引起了众多化学科研工作者的兴趣及关注.羰基化反应是合成含羰基化合物最有效的方法之一,CO作为现成的C1来源,它不仅价格便宜而且原子利用率高,并且可以有效地延长碳链.如今,羰基化反应在科研与工业上已经有了广泛的应用.据此,本文对近期关于过渡金属催化碳氢键活化羰基化领域的研究进展进行了综述,主要从sp,sp2和sp3碳氢键的活化羰基化反应3个部分进行了介绍,并对部分反应的机理进行了阐述.这些碳氢键活化羰基化反应为酸、酮、酯、酰胺、酸酐等羰基化合物的合成提供了简便和高效的途径.

Carbon monoxide can be used as an inexpensive and readily available C1 source, which is also in agreement with atom economy. Carbonylation reactions with CO have been and continue to be a very active area of research. Since the pioneering work of Heck in 1974, carbonylations of aryl halides and pseudohalides with CO have become one of the most common methods for the addition of a carbonyl group to organic molecules. Recently, transition-metal-catalyzed chelation-assisted carbonylation of C-H bonds for the synthesis of carbonyl compounds. The progress in carbonylation chemistry has been achieved in both academic laboratories and industry. Hence, in this paper, we have reviewed the research work of transition-metal-catalyzed C-H bond carbonylation reactions with CO in recent years. We made introductions of C-H bond carbonylation reactions from three main parts： sp C-H, sp2 C-H and sp3 C-H bond. Some reaction mechanisms were described in the paper. These C-H bonds carbonylation reactions provide a simple and effective method for the synthesis of acids, ketones, esters, amides and anhydrides.