The Sharpless asymmetric oxidation has been recognized as a versatile and useful synthetic method. We have already developed the method for preparation of chiral 2-furylmethanols by kinetic resolution of the racemates under the Sharpless reaction condition. As an application of this procedure to the synthesis of physiologically active natural products, an enantioselective synthesis of indolizidine alkaloid, swainsonine 4, a potent inhibitor of lysosomal α-mannosidase from Swainsona canescens, has been accomplished. The key feature ofthis synthesis was based on stereoselective construction of cis-fused oxabicyclononane 41 employing an intramolecular radical cyclization reaction, and a ring transformation into indolizidine skeleton by the Beckmann rearrangement. Furthermore, it has been realized that regio- and diastereo-selective oxidation of (E)-1-(2-furyl)but-2-en-1-ol 57 under the Sharpless reaction condition could be achieved depending on the chirality of DEPT used in the reaction. The procedure developed above was successfully appliedto the enantioselective synthesis of asperlin 66, isolated from Aspergillus nidulans, as a crystaline metabolite with antitumor and antibacterial activities.