Bio-inspired manganese-catalyzed deaminative hydroxylation of benzyl amines to corresponding alcohols.

Ji, Jiale; Wang, Shiliang; Dai, Zhaowen; Huo, Yinghao; Wang, Limin; Zheng, Qingshu; Tu, Tao · Nat Commun · 2025

basic_science · Level V

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Abstract

Direct conversion of amines to corresponding alcohols is challenging even under harsh reaction conditions. Inspired by enzymatic transamination, we present a transamination borrowing-hydrogen strategy that enables the direct and selective Mn-catalyzed deaminative hydroxylation of benzylamines, affording a broad scope (>30 examples) of alcohols in good yields at low catalyst loadings (down to 0.05 mol%). Notably, methanol serves a dual role as hydrogen donor and amino acceptor, rather than a conventional role as a methylating agent. Mechanistic investigations reveal base plays a pivotal role in facilitating the 1,3-proton transfer process, thereby effectively suppressing N-methylation pathways and favoring alcohol formation.