A 1,4,2-diazaborole-type heterocycle was obtained via addition of [(alkylamino)methyl]-trifluoroborate to 2H-azirine-2-carboxylate. The molecular structure of the product was confirmed by X-ray crystallog-raphy. The reaction proceeded at ambient temperature without metal catalysts and induced cleavage of the azirine C2-C3 bond without photoirradiation. This product can be regarded as a boron-containing peptidomimetic molecule that has potential applications in medicinal and synthetic chemistry.(c) 2022 Elsevier Ltd. All rights reserved.