Development of highly effective rhodium-catalyzed reaction and its application

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Development of novel highly chemo- and stereo-selective dirhodium(II)-catalyzed C-H insertion reaction of α-diazoketones controlled by stereo-electronic effect of tert-butyldimethosilyl group was achieved. As a result, a variety of functionalized cyclpentanones have been easily prepared. And the new acceleration method of the Baeyer-Villiger reaction of polysubstituted cyclopentanones was found to give polysubstituted δ-lactones. These new reactions applied to efficient syntheses of Corey lactone, an important intermediate of prostagrandins, and lactone portion of antitumor marine antibiotics discodermolide.A new methodology for the asymmetric synthesis of β-hydroxy acid was developed. Dirhodium(II)-catalyzed C-H insertion of α-alkoxydiazoketone, which was prepared from primary alkyl halide and readily available chiral α-hydroxy acid, gave stereoselectively 2,5-cis-disubstituted 3(2H)-furanone. The furanone was converted to chiral β-hydroxy acid with high optical purity.