Aromatic Metamorphosis of Indoles into 1,2-Benzazaborins.

Abstract

Among the plethora of aromatic compounds, indoles represent a privileged class of substructures that is ubiquitous in natural products and pharmaceuticals. While numerous exocyclic functionalizations of indoles have provided access to a variety of useful derivatives, endocyclic transformations involving the cleavage of the C2-N bond remain challenging due to the high aromaticity and strength of this bond in indoles. Herein, we report the aromatic metamorphosis of indoles into 1,2-benzazaborins via the insertion of boron into the C2-N bond. This endocyclic insertion consists of a reductive ring-opening using lithium metal and a subsequent trapping of the resulting dianionic species with organoboronic esters. Considering that 1,2-azaborins have attracted increasing academic and industrial attention as BN isosteres of benzene, the counterintuitive aromatic metamorphosis presented herein can feasibly be expected to substantially advance the promising chemistry of 1,2-azaborins.