Blue Light-Induced Diazo Cross-Coupling: Synthesis of Allyldiazo Compounds through Reshuffling of Functionalities

In this paper, we describe a new type of cross-coupling between simple diazo and vinyldiazo compounds that gives access to unusual allyldiazo products. Blue light discriminates two diazo compounds towards free carbene formation, triggering sequential cyclopropenation, (3+2) cycloaddition and ring opening rearrangement processes. This strategy involves an overall reshuffle of diazo functionality and olefinic carbons of vinyldiazo compounds with an extrusion of nitrogen. Mechanistic studies including a 15N-labelling experiment demonstrate that the diazo functionality of allyldiazo products derives from simple diazo compounds, while vinyldiazo reagents are selectively decomposed via energy transfer with thioxanthone photocatalyst. The obtained allyldiazo compounds can be efficiently converted into synthetically useful structures such as 1,3-dienes, gem-difluoro-1,4-diene, hydrazine, dihydropyrazole, pyridazine, and bicyclobutane.