Synthesis of Highly Functionalized 4-Iodo-7-azaindazoles via Condensation/Diels–Alder/Retro-Diels–Alder Cyclization of Iodoalkynones and 2-Hydrazineylpyrimidines

A method for the preparation of highly functionalized 4-iodo-7-azaindazoles is reported. These valuable heterocycles are synthesized via condensation of 2-hydrazineylpyrimidines with various iodoalkynones followed by Diels-Alder/retro-Diels-Alder cyclization. The method is general to the formation of products with a variety of C₃, C₅, and C₆ substituents while preserving the C₄ iodide functional handle for further late-stage functionalization. The utility of this transformation is demonstrated through the rapid synthesis of several bioactive azaindazole targets.