The innovative construction of novel N , O -bidentate ligands represents a long-standing challenge for chemists. Here, we report an unprecedented approach for the construction of N , O -bidentate derivatives via the merging of ring deconstruction with cycloaromatization of indolizines and cyclopropenones. Without any catalysts, our method can deliver a series of polyaryl 2-(pyridin-2-yl)phenols in excellent yields. In addition, N , O -bidentate organic BF 2 complexes can also be constructed via this one-pot protocol.