Phosphine‐Free Manganese(II)‐Catalyst Enables Acceptorless Dehydrogenative Coupling of Alcohols with Indoles

Herein, an air‐stable, molecularly defined NNN−Mn(II) pincer complex catalyzed acceptorless dehydrogenative coupling of alcohols with indoles is reported. A wide variety of symmetrical and unsymmetrical bis(indolyl)methane derivatives as well as some structurally important products such as Vibrindole A, Turbomycin B alkaloid, Antileukemic, and Anticancer agents were synthesized. Mechanistic studies illustrate the importance of the NH moiety in the complex and the crucial role of metal‐ligand cooperation during catalysis.