Described herein is the Rh(III)-catalyzed [3 + 2] annulations and C2-alkenylations of indoles with 1,3-diynes, which deliver the synthetically important 3H-pyrrolo[1,2-a]indol-3-ones and highly functionalized tetrasubstituted olefin derivatives. Importantly, in this methodology, the additive controlled selective formation of desired scaffolds. This synthetic strategy exhibits high efficiency and broad functional group compatibility. Furthermore, this protocol has been successfully extended to the synthesis of bisannulated and trisubstituted alkenes. The method is also smoothly applied for the synthesis of the core structure of protein kinase C inhibitor and melatonin analogues.