A well-defined phosphine-free metal-ligand cooperative route for -alkylation of aromatic amines activation of renewable alcohols catalyzed by NNN pincer cobalt(II) complexes.

This study presents the direct -alkylation of aromatic amines using greener primary alcohols as alkyl donors, catalyzed by base metal-derived Co(II) catalysts the borrowing hydrogen (BH) method. Two well-defined phosphine-free NNN-type pincer ligands (L1 and L2) were synthesized and utilized to prepare cobalt(II) catalysts C1 and C2. The catalysts were well characterized by UV-vis, IR, HRMS, and single-crystal X-ray diffraction studies. The catalysts C1 and C2 were utilized for the -alkylation of various aromatic, heteroaromatic as well as aromatic diamines, and a wide substrate scope total of 30 derivatives was explored with isolated yields up to 95%. Two antihistamine drug precursors for tripelennamine and mepyramine were synthesized on a gram scale for the large-scale applicability of the current protocol. Various control experiments were also performed to explore the possible reaction intermediates and reaction pathway. Cobalt(II) intermediates involved in the catalytic cycle were also characterized by the HRMS study.