A TiCl4-promoted cascade formal [3 + 2] cycloaddition/double
ring-opening/chlorination of 2-furylcyclobutanols with alkyl or aryl
azides is described. This highly efficient transformation involves
the formation/cleavage of several C–N, C–Cl, C–C,
and C–O bonds in a single operation. It enables the quick construction
of trisubstituted 1,2,3-triazoles with an (E)-enone
moiety and a 3-chloropropyl unit. The chlorinated products are readily
transformed into other structurally diverse analogues.