68. Regioselective Synthesis of Tetrasubstituted Benzenes via Co-Catalyzed Cycloaddition of Alkynyl Ketones and 2-Acetylpyridines

Yin, L.; Xu, M.; Wang, Y.; Xie, H.; Yuan, Y.; Wang, C.;* Jiang, Y.-Y.;* Li, Y.*  J. Org. Chem. 2021, 86, 12158-12167. Download Link

Abstract: A Co(II)-catalyzed cycloaddition reaction of alkynyl ketones and 2-acetylpyridines using 2,2′-bipyridine as the ligand has been developed. These reactions have been realized through Co-catalyzed reductive coupling of two molecules of 2-acetylpyridine followed by regioselective insertion of the alkynone. It is the first example of regioselective cyclotrimerization of one molecule of alkyne and two molecules of monoketone to polysubstituted benzene derivatives in good to excellent yields. A mechanism involving the formation of a cobaltacyclopentane via homocoupling of 2-acetylpyridines is proposed, and it is supported by the DFT calculations.