An efficient and highly stereoselective approach towards a new type of branched-chain pentahydroxylated pyrrolizidine 7 from a D-glucose isothiocyanate scaffold has been developed. The key features of this strategy are the construction of a diene-substrate foldamer possessing an amino functional group followed by subsequent ring-closing metathesis, an intramolecular cyclisation readily induced by regioselective tosylation to establish the pyrrolizidine unit and a highly diastereoselective, substrate-controlled dihydroxylation. (C) 2016 Elsevier Ltd. All rights reserved.