Arenes participate in 1,3-dipolar cycloaddition with in situ-generated diazoalkenes

The venerable 1,3-dipolar cycloaddition has been widely used in organic synthesis for the construction of various heterocycles. However, in its century-long history, the simple and omnipresent aromatic phenyl ring has remained a stubbornly unreactive dipolarophile. Here we report 1,3-dipolar cycloaddition between aromatic groups and diazoalkenes, generated in situ from lithium acetylides and N-sulfonyl azides. The reaction results in densely functionalized annulated cyclic sulfonamide-indazoles that can be further converted into stable organic molecules that are important in organic synthesis. The involvement of aromatic groups in the 1,3-dipolar cycloadditions broadens the synthetic utility of diazoalkenes, a family of dipoles that have been little explored so far and are otherwise difficult to access. The process described here provides a route for the synthesis of medicinally relevant heterocycles and can be extended to other arene-containing starting materials. Computational examination of the proposed reaction pathway revealed a series of finely orchestrated bond-breaking and bond-forming events that ultimately lead to the annulated products.