Total synthesis of ()-kaitocephalinElectronic supplementary information (ESI) available. See DOI: 10.1039/c3cc42365d

()-Kaitocephalin has been synthesized. With the C9 stereocenter from Garner's aldehyde, the C4 quaternary carbon was installed by the desymmetrization of the Cbz-protected serinol. The remaining stereogenic centers were generated through mercuriocyclization, epoxidation and regioselective epoxide opening, in which the quaternary carbon most likely played crucial roles in the stereoinduction. Total synthesis of ()-kaitocephalin has been completed through desymmetrization for the quaternary carbon, mercuriocyclization for the pyrrolidine, epoxidation followed by epoxide opening for the amino hydroxy functionality and concurrent oxidation for the three carboxylic acids.