An investigation into the sensitivity of reaction conditions to a highly utilized protocol has been reported, wherein the mono-Boc functionalization of prolinol could be controlled for the exclusive synthesis of either N-Boc, O-Boc, or oxazolidinone derivatives. Mechanistic investigation revealed that the elementary steps could possibly be controlled by (a) a requisite base to recognize the differently acidic sites (NH and OH) for the formation of the conjugate base, which reacts with the electrophile, and (b) the difference in nucleophilicity of the conjugate basic sites. Herein, a successful chemoselective functionalization of the nucleophilic sites of prolinol by employing a suitable base is reported. This has been achieved by exploiting the relative acidity difference of NH and OH along with the reversed nucleophilicity of the corresponding conjugate bases N- and O-. This protocol has also been used for the synthesis of several O-functionalized prolinol derived organocatalysts, few of which have been newly reported.