关键词: 碳水化合物, 手性膦, 脱硼烷, 铂(II)化合物

Via four steps of nucleophilic ring-opening of α-D-manno-epoxide with Ph2P－ anion, adduction of boranes to phospnine, methylation of hydroxyl, and deprotection of the phosphine-boranes adduct, afforded the desired methyl 3-deoxy-3-diphenylphosphino-2-O-methyl-4,6-O-phenylmethenyl-α-D-pyranoaltroside (5) in 55% of yield. It was found that: (1) the adduct of boranes to the carbohydrate-based phosphine was formed smoothly in the presence of alkyloxide, (2) the alkoxide derived from the secondary alcohol of pyranoside was methylized with MeI as in its sodium salt other than in lithium salt in THF at room temperature, and (3) the deprotection of boranes from the carbohydrate-based phosphine adduct went smoothly by several of organic bases, but more efficiently by ethanol. The corresponding cis- and trans-[Pt(5)₂Cl₂] formed by the reaction of the carbohydrate-based phosphine 5 with cis- and trans-[Pt(NCMe)₂Cl₂], respectively. The coupling constant 1JPt-P was reliable to assign the configuration of the geometrical stereoisomers of Pt(II) complexes with the carbohydrate-based phosphine.

Key words: carbohydrate, chiral phosphine, deboronation, Pt(II) complex