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One-carbon homologation reactions based on one-carbon insertion into the N−O bond of heterocycles have received tremendous interest over the past decades. However, these protocols have to rely on the use of hazardous and not easily accessible diazo compounds as precursors, and examples of the relevant asymmetric catalysis have not been reported. Here we show that a copper-catalyzed intermolecular formal (5 + 1) annulation of 1,5-diynes with 1,2,5-oxadiazoles involving one-carbon insertion into the heterocyclic N−O bond via non-diazo approach. This method enables practical and atom-economic synthesis of valuable pyrrole-substituted oxadiazines in generally moderate to good yields under mild reaction conditions. In addition, the possibility of such an asymmetric formal (5 + 1) annulation also emerges. One-carbon insertion into N–O bonds is widely exploited in organic synthesis, but synthetic protocols for this rely on hazardous diazo precursors that are difficult to access. Here, copper-catalyzed intermolecular formal (5 + 1) annulation of 1,5-diynes with 1,2,5-oxadiazoles is shown to facilitate one-carbon insertion into heterocyclic N–O bonds without the need for diazo precursors. [ABSTRACT FROM AUTHOR]