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Control experiments: (A) Thermal rearrangement of 1 affords the N−O bond formation product. (B) Deprotonation of oxadiazolone deactivates reaction. (C) Methylated oxadiazolone undergoes N−O bond formation. (D) Aldoxime and chlorinated analogue undergo neither N−O bond formation nor Tiemann‐type rearrangement.
