Corynantheine-type alkaloids are major components of the Mitragyna speciosa, also known as kratom, that exhibit unique pharmacological activity. However, no universal method to prepare these alkaloids has been reported. Disclosed herein is a catalytic, asymmetric platform that enables rapid access to corynantheine alkaloids. The first enantioselective total synthesis of (-)-corynantheidine pseudoindoxyl is described. The first asymmetric syntheses of (+)-corynoxine and (-)-corynoxine B were also achieved, along with enantioselective syntheses of (-)-corynantheidol and (-)-corynantheidine. Through this work, all series of corynantheine alkaloids including indole, spirooxindole, and pseudoindoxyl can now be accessed in the laboratory, enabling comprehensive biological investigation of kratom alkaloids to be undertaken.