A practical strategy has been developed for delivering 2,6-dideoxy sugars and uncommon sugars with 4-substitution. This strategy employed Ferrier rearrangement reaction and BF 3 ·OEt 2 -induced peroxidation to construct key intermediates 2,3-unsaturated glycosides and α,β-unsaturated lactones from peracetyl rhamnal. After further derivatization, four uncommon sugars with 4-substitution and eight uncommon sugar units with 3,4-disubstitution were successfully synthesized.