Using Methanol as a Formaldehyde Surrogate for Sustainable Synthesis of N ‐Heterocycles via Manganese‐Catalyzed Dehydrogenative Cyclization

Comprehensive Summary The development of an efficient and sustainable synthetic route for formaldehyde production from renewable feedstock, especially in combination with a subsequent transformation to straightforwardly construct valuable chemicals, is highly desirable. Herein, we report a novel manganese-catalyzed dehydrogenative cyclization of methanol as a formaldehyde surrogate with a variety of dinucleophiles for facile synthesis of N-heterocycles. The in situ generated formaldehyde via catalytic methanol dehydrogenation can be selectively trapped by diverse dinucleophiles to avoid several possible side reactions. The utility of this transformation is further highlighted by its successful application to the synthesis of C-13-labeled N-heterocycles using (CH3OH)-C-13 as a readily accessible C-13-isotope reagent.