Understanding Catalyst Activation Drives Transition from Iridium to Manganese Catalyzed Hydrogen Autotransfer Chemistry

As an alternative to iridium catalysts, a procedure to access and employ a more earth-adundant Mn₂(CO)₁₀-derived pincer complex was successfully demonstrated in the synthesis of a complex pharmaceutically relevant ketone from milligram to 500g scales. Mechanistic studies revealed that the dissociation of CO driven by light is a critical step in forming the active catalyst. This robust and mechanistically informed method reliably promotes hydrogen autotransfer of alcohols, catalyzing a diverse array of C-C and C-N bond formations. This emphasizes the importance of precatalyst selection and understanding catalyst activation to enable rapid and successful uptake of novel methods in sustainable catalysis.