Since the seminal work of Trost and coworkers, metal-catalyzed enyne cycloisomerization has been developed with remarkable achievements. This transformation proceeds with quantitative atom economy. A variety of methods has been demonstrated to deliver diverse cyclic products under the catalysis of a range of metal complexes and salts. We have begun exploring enyne cycloisomerizations via alkyne activation catalyzed by π acid metals. To develop new protocols of producing enantioenriched cycloisomerization products, a chirality transfer approach has been demonstrated giving superb enantiospecificity. With our interests in the total synthesis of gelsemium alkaloids, we investigated both chirality transfer approach and asymmetric catalysis approach to produce the enantioenriched core structure. Enynes with an oxygenated substituent protected by various groups were tested. The substituent that dictates enantiospecificity ends up incorporated at the bridgehead position was proved to be removable via Barton decarboxylation. The realize of this idea provides the breadth to induce the enantioselectivity in gelsemium alkaloids total synthesis. There enynes were insufficiently effective for now, however. The investigation of an asymmetric catalysis approach using bisphosphine-Au system proved more fruitful. The core structure with 97% ee has been achieved. We have also studied chirality transfer of N-tethered enynes in the cycloisomerization reactions. A protecting group for the nitrogen atom is essential for the transformation. The combination of methyl carbamate and Et at the propargylic position can induce superb enantiospecificity and good yields under the catalysis of JohnPhosAu(MeCN)SbF6.