Unrestricted.2016-11-142010-12-012016-11-142010-12http://hdl.handle.net/2346/ETD-TTU-2010-12-1240As water possesses many ideal characteristics for a reaction medium such as accessibility, environmental safety, and low cost, the development of organic reactions in aqueous media has been of central importance in recent organic chemistry. Since many organic compounds have limited solubility in water, efficient water-mediated reactions with high selectivities and reactivities are still somewhat rare, and hence there is a need for organic methodological development in mainly water media. The desymmetrization of meso compounds is a powerful concept with regards to both asymmetric and nonasymmetric synthesis. Half-esters produced by desymmetrization of symmetric diesters are especially versatile building blocks in organic synthesis. In this dissertation, the syntheses of various half-esters from the corresponding diesters via monohydrolysis, which is a desymmetrization reaction, in mainly water media are discussed. The highly selective monohydrolysis of dialkyl malonates and their derivatives are discussed. In the second chapter, the reactions are practical, yielding the corresponding half-esters in high yields in a straightforward manner without inducing decarboxylation. The hydrophobicity of diester substrates was found to be one of the factors which could determine the selectivity in monohydrolysis reactions. The high exo-facial selectivity observed in the selective monohydrolysis of a series of near-symmetric diesters is described in the third chapter. The selectivities were found to be specific, although the reaction center in these reactions is one covalent bond distant from the norbornane or norbornene ring, where the difference of the environment between the exo face and endo face is expected to be negligible. In addition to these experimental studies, the conformational studies in symmetric diesters showed electronic interaction between the two carbonyl groups via computational calculations in the fourth chapter. The stable structures of symmetric diesters with attractive interaction on the two carbonyl groups are presented. This conformational preference is expected to contribute to the high selectivities in the monohydrolysis of symmetric diesters. The asymmetric monohydrolysis of symmetric diester is also investigated with chiral ionic liquids in the last chapter. Since the reactivity of selective monohydrolysis of symmetric diesters with an alkali base could be affected on the choice of co-solvents, the chiral ionic liquids can influence the chirality of half-ester by selective monohydrolysis. The studies to improve the enantiomeric excesses of half-esters by the modification of substrates and chiral ionic liquids are underway.application/pdfengDesymmetrizationMonohydrolysisHalf-estersMonoalkyl malonate derivativesBicyclic half-estersDissertation