Stereoselective reactions of esters/amides and their surrogates catalyzed by bifunctional organocatalysts and enantioselective separation of secondary alcohols by hydrogenbonded organic framework

Ester and amide are among the most common and important functionalities in the organic synthesis of bioactive molecules. However, due to the high pKa value of the alpha-proton in the ester and amide compounds, a general asymmetric catalytic methodology for the direct activation of ester or amide is still elusive. To obtain the desired products via asymmetric catalysis, various masked synthetic equivalents of ester/amide (surrogates) have been designed in the past decades. The first chapter of this dissertation describes my doctoral research on the organocatalyzed stereoselective reactions of esters/amides and their surrogates, namely, the organocatalyzed reactions of modified N-acyl oxazolidinones and thioesters for the enantioselective synthesis of cyclic thiocarbamates with a spirooxindole moiety and N-protected beta-amino thioesters, respectively; the novel application of acetylphosphonates as ester/amide surrogates in asymmetric catalysis, such as the organocatalyzed aldol reaction and Michael reaction; and the direct employment of unactivated esters in organocatalyzed carbon-carbon formation reactions.;The second chapter of this dissertation describes my contribution to the enantioselective separation of secondary alcohols by using hydrogen-bonded organic frameworks, which provides an efficient and economic method for the resolution of racemic secondary alcohols.