PNP-Mn(I) Catalyzed Base Free -Alkylation of Amines Using Alcohols.

We report a Mn(I) pincer complex, [Mn(CO){-PhPCHC(O)N(CHPPh-)}κ-,,], bearing an amide-functionalized bisphosphine (BalaHariPhos), for the efficient -alkylation of amines with alcohols. The reaction proceeds under base-free conditions at 80 °C, affording -alkylated products in good to excellent yields within 12 h. Broad substrate scope is demonstrated, including the synthesis of indoles and dibenzyl piperazine. Selective mono--methylation of amines using methanol as a C source was also achieved. This work establishes a sustainable, non-noble metal platform for amine functionalization.