Synthesis of Functionalized Bicyclo[3.1.0]hexanes from Aucubin: An Access to Fused Aminocyclopentitols

Treatment of iodolactone 8a , having a cyclopentano[c]pyran skeleton and deriving from aucubin ( 1 ) (Scheme 1), with sodium trimethylsilanolate permitted a straightforward rearrangement to bicyclo[3.1.0]hexenes 10a and 10b (Schemes 3 and 4). Introduction of an N‐atom via a modified Curtius reaction provided an easy entry to fused aminocyclopentitols (Schemes 4 and 5). Target 4 is a conformationally restricted cyclopropane‐fused analogue of the glycosidase inhibitors mannostatins A ( 2 ) and B ( 3 ).