糖質を基盤とする柔軟な不斉空間の開拓と代謝機構化学への応用

抄録

Carbohydrates are important sources of chirality in organic synthesis. We became aware of possible stereocontrol elements, in which the intrinsic molecular architecture of a carbohydrate serves as a template for chirality transcription.
Oxidation of diacetone-D-glucose affords 1, 2 : 5, 6-di-O-isopropylidene-α-D-ribo-hexos-3-ulose 1. Each of α- and β-substituents introduced onto the C-3 carbonyl group of 1 must sterically interact with the bulky α-oriented 1, 2-isopropylidene group and the β-oriented substituent at C-4, respectively. These steric interactions may dictate the conformation of the substituents, thereby controlling stereochemistry of reactions on the chiral template 1. Highly enantioselective synthetic method of chiral monodeuterated glycerol, chiral deuterated glycines, chiral amino acids, (2R, 3S) -3-alkylmalic acid, as well as mevalonolactone based on the chiral template 1 and its application to biochemical studies are described.