N-formyl compounds have broad synthetic utility, serving as starting materials in allylation, reduction, and hydrosilylation reactions, among others. Here, we present the novel creation of N-formyl compounds using 1,4-dioxane as the formylation agent. Several primary and secondary amines were successfully formylated in the presence of 1,4-dioxane and catalytic silver hexafluoroantimonate(V). Additionally, substantial formylation of 1-(phenylmethyl)-2-imidazolidinone was achieved in the presence of 12-Crown-4 (74% yield), while a low degree of formylation was observed with 15-Crown-5 (6% yield). No formylation was seen with 18-Crown-6. These results suggest the existence of a previously undiscovered route to N-formyl synthesis contingent on the presence of, but limited by the ring size of, multimeric ethylene oxide.

Dioxane-mediated N-formylation

253rd National Meeting (2017)

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