13 糖類の化学変換 : トリアルキルスズ基によるヒドロキシル基及びチオール基の活性化と不活性化

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Recently silylated organic molecules have been extensively employed in organic reactions in order to modify the reactivity of original molecules in the field of carbohydrates and nucleoside chemistry. In this report we described both mild and specific transformations of carbohydrates based on the reactivity of trialkylstannylated compounds. [I] O-Glycoside Synthesis: a) Lewis Acid Catalysed Method; Reaction of acetobromoglucose 1 with tri-n-butylstannyl alkoxides in the presence of equivalent amount of Lewis acid gave corresponding O-glycosides in good to fair yields. (see Table 1) b) Modified Koenigs-Knorr Method; Reaction of 1 with tri-n-butylstannyl alkoxides inthe presence of silver salts such as AgBF_4 gave corresponding β-glycosides in good yields. c) 1,2-cis Glycoside Synthesis; Reaction of 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl chloride with tri-n-butylstannyl alkoxides in the presence of halide anion gave α-glycosides such as 3 or 4 in reasonable yields. d) Orthoester Method; Reaction of acetohalogenoses such as 1, 11,13 with stannylated alkoxides in the presence of bromide anion gave good yields of orthoesters. (see Table 2) e) O-Glycosyl Ester Synthesis; Reaction of 1 with trialkylstannyl carboxylic esters in the presence of bromide anion gave corresponding O-glycosyl esters in good yields. [II] S-Glycoside Synthesis: The reaction of readily available tri-n-butylstannyl alkylsulfides with acetbromoglucose 1 in the presence of Lewis acid gave good yields of the mixture of α and β-thioglycosides. By employing peracylated mono- and di-saccharides in stead of halosugar high yields of thioglycosides could be obtained in a stereo-specific manner. (see Table 3 and 4)
天然有機化合物討論会の論文
1976-09-20

13 糖類の化学変換 : トリアルキルスズ基によるヒドロキシル基及びチオール基の活性化と不活性化

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