Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho ‐Nitro‐haloarenes coupled with vinylic N ‐methyliminodiacetic acid (MIDA) boronates generate ortho ‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho ‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.