DMF as CO Surrogate in Carbonylation Reactions: Principles and Application to the Synthesis of Heterocycles

Abstract

Transition metal-catalyzed carbonylation reactions have emerged as one of the most relevant synthetic approaches for the preparation of carbonyl-containing molecules. The most commonly used protocol for the insertion of a carbonyl moiety is the use of carbon monoxide (CO) but, due to its toxic and explosive nature, this process is not suitable at an industrial scale. More recently, the chemistry of CO surrogates has received large attention as a way to use less expensive and more environmentally friendly methods. Among the various CO surrogates, N,N-dimethylformamide (DMF) has been paid greater attention due to its low cost and easy availability. This mini-review gives appealing insights into the application of DMF as a CO surrogate in metal-catalyzed carbonylations; in particular, in the first part we will give a general state of the art of these reactions for the preparation of carbonyl-containing molecules; then, we will take into account all the various synthetic approaches for the metal-catalyzed carbonylative synthesis of heterocycles using DMF as a CO surrogate. Each protocol has been discussed critically in order to screen the best synthetic method and to offer perspective on trends and future directions in this field.