Regioselective SN2 reactions for rapid syntheses of azido-inositols by one-pot sequence-specific nucleophilysisElectronic supplementary information available: Synthetic procedures and characterization, and crystal structures. CCDC 1532602-1532609. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7cc01219e

Triflates of myo -inositol undergo facile solvolysis in DMSO and DMF yielding S N 2 products substituted with O -nucleophiles; DMF showed slower kinetics. Axial O -triflate undergoes faster substitution than equatorial O -triflate. By exploiting this difference in kinetics, solvent-tuning and sequence-controlled nucleophilysis, rapid synthesis of three azido-inositols of myo -configuration from myo -inositol itself has been achieved. Sequential nucleophilysis of myo -inositol-disulfonate provides easy access to azido-inositols.