Ruthenium-Catalyzed Dehydrogenative Functionalization of Alcohols to Pyrroles: A Comparison between Metal-Ligand Cooperative and Non-cooperative Approaches.

Abstract

Herein, we report the synthesis and characterization of two ruthenium-based pincer-type catalysts, [1]X (X = Cl, PF6) and 2, containing two different tridentate pincer ligands, 2-pyrazolyl-(1,10-phenanthroline) (L1) and 2-arylazo-(1,10-phenanthroline) (L2a/2b, L2a = 2-(phenyldiazenyl)-1,10-phenanthroline; L2b = 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline), and their application in the synthesis of substituted pyrroles via dehydrogenative alcohol functionalization reactions. In catalyst [1]X (X = Cl, PF6), the tridentate scaffold 2-pyrazolyl-(1,10-phenanthroline) (L1) is apparently redox innocent, and all the redox events occur at the metal center, and the coordinated ligands remain as spectators. In contrast, in catalysts 2a and 2b, the coordinated azo-aromatic scaffolds are highly redox-active and known to participate actively during the dehydrogenation of alcohols. A comparison between the catalytic activities of these two catalysts was made, starting from the simple dehydrogenation of alcohols to further dehydrogenative functionalization of alcohols to various substituted pyrroles to understand the advantages/disadvantages of the metal-ligand cooperative approach. Various substituted pyrroles were prepared via dehydrogenative coupling of secondary alcohols and amino alcohols, and the N-substituted pyrroles were synthesized via dehydrogenative coupling of aromatic amines with cis-2-butene-1,4-diol and 2-butyne-1,4-diol, respectively. Several control reactions and spectroscopic experiments were performed to characterize the catalysts and establish the reaction mechanism.