We hypothesized that the B-N to B-C substitution could be made through the addition of stabilized carbon nucleophiles to N-alkylnitrilium cyanoboranes. Alkyl 2-pyridylacetates can be deprotonated using organometallic bases in a facile manner and subsequently alkylated at the benzylic methylene position. Methyl 2-pyridylacetate 2a was deprotonated by n-butyllithium at -78°C, followed by the addition of a solution of nitrilium 4 in dichloroethane and warming to room temperature. Chromatographic purification of the reaction mixture afforded borindolizine 3a in a 51% yield as a highly blue-fluorescent solid (Figure ). Spectroscopic analysis of 3a in dichloromethane showed a blue fluorescent λmax,em at 438 nm (λmax,abs = 289 nm, 378 nm) with a high Stokes shift (362 cm -1 ), which is red-shifted from boramidine 1 (R = H) with a λmax,em at 392 nm. Borindolizine 3a was crystallized from dichloromethane followed by X-ray analysis which shows a highly planar structure that incorporates an intramolecular hydrogen bond between the aniline-like N-H and the ester C=O (see Supporting Information). The compound is bench-stable over an extended period and can be stored under ambient conditions.