As important building blocks for the syntheses of bio-organic compounds, such as alkaloids, macrocyclic antibiotics, pheromones, antileukemics and flavor components, the syntheses of polyfunctional, enantiomerically pure lactone and lactam skeletons have attracted substantial attention. We report a highly efficient Rh-catalyzed cycloisomerization, which is a powerful method for the preparation of a variety of functional lactones and lactams in high yield and excellent ee values. In addition, a combination of a kinetic process and cycloisomerization will be presented for the preparation of polyfunctional g-substituted lactones and lactams in high yield and excellent enantioselectivity.