Alkynyl Fischer Carbenes as a Platform for the Production of Difluorodiazaborinine Complexes via β‐Amino‐azadienes

The results of a study of the reactivities of alkynyl Fischer carbenes in the syntheses of diazaborinine derivatives 7a‐i are reported. The strategy employed included the use of β‐amino‐α,β‐unsaturated carbenes ( 3a–j ) with different amines in order to determine the scope of a previously unknown catalytic reaction in the presence of copper salts and anilines. The reaction was highly stereoselective, yielding ( Z )‐isomers of the β‐amino‐1‐azadiene framework as the main products ( 4a–o ). As an extension of this research, the compounds 4a–o proved to be suitable precursors for the syntheses of diazaborinine scaffolds in good yields ( 7a‐i ).