An indolizidine alkaloid, (−)-8a-epi-lentiginosine was synthesized from d-glucose using the Pd-BiPhePhos catalyzed intramolecular Tsuji–Trost reaction of non−derivatized allylic alcohol as a key construction of the hydroxylated pyrrolidine ring to give the desired product in good yield and high stereospecificity (dr = 97:3). The absolute configuration and structure of (−)-8a-epi-lentiginosine were confirmed by NMR and X-ray crystal structure analysis. The crystal structure of (−)-8a-epi-lentiginosne showed the envelope conformation of the five-membered ring, which is an N-atom in the endo-position, and the fused six-membered ring adopts a chair conformation similar to the DFT optimized structure. The solid-state packing is dominated by a 1D-hydrogen-bonded network along the a-axis involving both hydroxyl groups and the amine. The large HOMO–LUMO energy gap indicated the high stability of the compound.