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Chiral α-monofluorocarbonyl compounds have recently received much attention and have been often employed as targets for asymmetric synthesis. However, there are relatively few reports describing applications of such compounds compared to other types of organofluorine compounds such as trifluoromethylated compounds and fluoroaromatics in spite of the many potential applications of such compounds. We describe here our recent results regarding examination of use of several chiral α-monofluorocarbonyl compounds for determination of absolute configurations of chiral compounds and clarification of biological roles of stereochemistry of important medicinal agents.