Biochemical transformations with microbes and enzymes have been utilized to produce important natural products for human life. Because of its high stereoselectivity and rather loose substrate specificity, it is extremely useful process to prepare chiral building blocks starting from designed substrate molecules for the synthesis of biologically active substances. The process includes mainly functional group modifications such as reduction, oxidation, hydrolysis and esterification and so on, and there have been so many successful reports in this area. As so many excellent review articles have been published, this review deals only with asymmetric reduction of cyclic diketones and keto-esters with yeasts especially baker's yeast to afford useful chiral building blocks and representative examples of their applications to organic synthesis.