Highly Selective Synthesis of Seven-Membered Azaspiro Compounds by a Rh(I)-Catalyzed Cycloisomerization/Diels–Alder Cascade of 1,5-Bisallenes

[Image: see text] The synthesis of spiro compounds featuring seven- and six-membered rings in the spirobicyclic motif is successfully achieved through a cascade process encompassing a rhodium(I)-catalyzed cycloisomerization followed by a highly selective Diels–Alder homodimerization. The scope of the reaction is analyzed based on a series of synthetic substrates, and control experiments and DFT calculations led us to justify the exquisite degree of selectivity observed.