Nickel catalyzed sustainable synthesis of benzazoles and purines via acceptorless dehydrogenative coupling and borrowing hydrogen approach

Herein we report nickel-catalyzed sustainable synthesis of a few chosen five-membered fused nitrogen heterocycles such as benzimidazole, purine, benzothiazole, and benzoxazole via acceptorless dehydrogenative functionalization of alcohols. Using a bench stable, easy to prepare, and inexpensive Ni(ii)-catalyst, [Ni(MeTAA)] (1a), featuring a tetraaza macrocyclic ligand (tetramethyltetraaza[14]annulene (MeTAA)), a wide variety of polysubstituted benzimidazole, purine, benzothiazole, and benzoxazole derivatives were prepared via dehydrogenative coupling of alcohols with 1,2-diaminobenzene, 4,5-diaminopyrimidine, 2-aminothiphenol, and 2-aminophenol, respectively. A wide array of benzimidazoles were also prepared via a borrowing hydrogen approach involving alcohols as hydrogen donors and 2-nitroanilines as hydrogen acceptors. A few control experiments were performed to understand the reaction mechanism.

Automated summary

In this study, a nickel-catalyzed sustainable synthesis method was utilized to prepare a variety of five-membered fused nitrogen heterocycles, including benzimidazole, purine, benzothiazole, and benzoxazole. This was achieved through acceptorless dehydrogenative functionalization of alcohols and borrowing hydrogen approach, using a bench stable, easy to prepare, and inexpensive Ni(ii)-catalyst. Control experiments were conducted to elucidate the reaction mechanism.