A reagent-directed divergent synthesis of three skeletally distinct compounds, namely, amino-substituted indolizidine alkaloids, decahydropyrazino[2,1,6-cd]-pyrrolizine triols and (–)-pochonicine stereoisomers have been accomplished from a single precursor. Tri-O-benzyl-d-glucal was converted into a diastereomeric mixture of homoallylic alcohols through a seven-step sequence developed earlier in our lab. Intramolecular iodo-amination of the homoallylic alcohols proceeded through a 5-exo-tet ring opening of initially formed iodonium ion to give the iodo-substituted pyrrolizidine {[5,5-]-fused} derivatives. Upon exposure to AgOAc, these iodo-pyrrolizidines underwent a ring enlargement under the reaction condition and delivered polyhydroxylated indolizidine {[5,6]-fused} derivatives as the main products. On the other hand, when the iodo-pyrrolizidines were treated with NaH, a smooth intramolecular substitution reaction took place resulting in the formation of novel decahydropyrazino[2,1,6-cd]pyrrolizine triols in good yields. Diversely, epoxidation of the homoallyic alcohols followed by intramolecular ring opening and subsequent synthetic transformations delivered stereoisomers of (–)-pochonicine. The structure and stereochemistry of the final compounds were established through detailed 2D-NMR analysis. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim