Cross-coupling reactions of nickel catalysts have made series progress

In the research field of modern organic reaction new methodology, the cross-coupling reaction catalyzed by cheap nickel as a catalyst is one of the hot spots, especially in the Suzuki coupling reaction, many innovative results have been reported. However, there are still a large number of scientific problems that need to be resolved: First, the coupling reaction of phenolic compounds activated with phosphine/phosphorus groups cannot be performed; secondly, in the reaction of other substrates reported, Most reactions have the disadvantages of large amounts of catalyst and poor stability, especially for several types of substrates that are low in reactivity but inexpensive and widely available, such as chlorinated aromatics, aryl sulfonates, and sulfamates. Up to 5 mol% of catalyst, but also need to add at least one-fold amount of phosphine ligand. Such problems as mentioned above seriously hinder the practical application of nickel-based catalysts.

The research team of Han Fushen of the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, is devoted to the research of new methods for the cross-coupling reactions of carbon-carbon and carbon-heteroatoms catalyzed by nickel catalysts. In recent years, a series of advances have been made in this field. By designing new catalysts and activation principles, the Suzuki-Miyaura cross-coupling reaction of phenolic compounds activated with phosphorus/phosphine with NiCl2(dppp) as a catalyst and boronic acid was realized for the first time (Chem. Eur. J., 2010, 16 , 4991; Chem. Eur. J., 2011, 17, 4038; Chem. Commun., 2011, 47, 12840), research results by Chem. Rev., 2011, 111, 1346; Chem. Soc. Rev., 2011 , 40, 5170 and Chem. Eur. J., 2011, 17, 1728, etc. conducted a graphic review. On this basis, the research group also achieved high-efficiency Suzuki-Miyaura cross-coupling reaction of aryl chlorides, phenol sulfonates and sulfonamides and other inert substrates with boric acid. The amount of catalyst is less than 1%, and no need to add any additives. body.

The research results published a series of papers (Adv. Synth. Catal., 2011, 353, 1543; Adv. Synth. Catal., 2011, 353, 309; Eur. J. Org. Chem., 2012, 3575), patent 3 Items, of which 1 has been authorized. This method has a good practical application prospect in the synthesis of some important drugs and material intermediates. Recently, they have also realized new methods for efficient C–P bond formation of nickel-catalyzed halogenated aromatics and phenolic compounds (Chem. Commun., 2012, 48, 5868; Chem. Eur. J., 2012, 18, 9622). .

The above results have aroused widespread concern in the field, and the project leader was invited to publish a review article on Chem. Soc. Rev. (2013, 42, 5270), which is to carry out the latest research progress in the related field with nickel as a catalyst. Commentary.

The project was supported by the start-up funds for the “Hundred Talents Program” of the Changchun Institute of Applied Chemistry at the Chinese Academy of Sciences, the “Hundred Talents Program” project of the Chinese Academy of Sciences and the Open Fund of the National Key Laboratory of Fine Chemicals.