Major increases of the selectivity and/or reactivity in aminosugar and sugar O-alkylation were observed in the presence of tetrabutylammonium fluoride (TBAF) in comparison to TBAI under phase-transfer conditions or in solution. The presence of TBAF allowed the selective and rapid alkylation of the 6-hydroxyl function of neamine and efficient preparation of protected intermediates useful in synthesis and potent or potential antimicrobial O-alkylated derivatives of neamine and paromamine. In regard to the observed strong effects of TBAF, the alkylation and acylation of carbohydrates merit to be studied in the presence of TBAF under phase-transfer conditions.