Ring-opening of chiral glycidol or glycidyl tosylate by Me3SiN3 or Me3SiCN catalyzed by Ti(O-i-Pr)4 or Al(O-i-Pr)3 occured in a regiospecific manner and with very high stereoselectivity, leading to new trifunctionalized chiral building blocks. The enantiomeric excess of the ring-opened products was 90-95 %, as determined by H-1 NMR of the Mosher ester derivatives, indicating that there was not significant loss of optical purity during the ring-opening. This methodology was applied for the one-pot synthesis of (R)-1-azido-3-naphthyloxy-2-hydroxypropane in 94 % ee, a precursor of analogs of propanolol.