通过使用三（三甲基甲硅烷基）[2H]硅烷实现2'-脱氧[2'-2H]核糖核苷衍生物的高非对映选择性合成。
Highly diastereoselective synthesis of 2'-deoxy[2'-2H]ribonucleoside derivatives by the use of tris(trimethylsilyl)[2H]silane.
作者信息
Kawashima E, Uchida S, Ishido Y
机构信息
Laboratory of Pharmaceutical Chemistry, School of Pharmacy, Tokyo University of Pharmacy and Life Science, Japan.
出版信息
Nucleic Acids Symp Ser. 1997(37):47-8.
The use of (Me3Si)3SiH or (Me3Si)3Si2H-Et3B system in place of Bu3SnH or Bu3Sn2H-Et3B system for a reductive protylation or deuteration reaction of 2'-Br-2'-deoxy-3',5'-O-TIPDS-[2'-2H]ribonucleosides or 2'-Br-2'-deoxy-3',5'-O-TIPDS-ribonucleosides was confirmed to improve the reactions to afford an excellent diastereoselectivity, i.e., the diastereoselectivity of (2'S)- or (2'R)-2'-deoxy-[2'-2H]ribonucleosides obtained by the reaction at 0 degree C is equivalent to the diastereoselectivity obtained by that using Bu3SnH or Bu3Sn2H-Et3B system at < -70 degrees C; the reductive deuteration of 2'-O-phenoxythiocarbonyl-3',5'-O-TIPDS-ribonucleosides through (Me3Si)3Si2H-Et3B system at 0 degree C also gave (2'R)-2'-deoxy[2'-2H]ribonucleosides with such a high diastereo-selectivity as above.
已证实，使用(Me3Si)3SiH或(Me3Si)3Si2H-Et3B体系代替Bu3SnH或Bu3Sn2H-Et3B体系用于2'-Br-2'-脱氧-3',5'-O-TIPDS-[2'-2H]核糖核苷或2'-Br-2'-脱氧-3',5'-O-TIPDS-核糖核苷的还原质子化或氘代反应，可改善反应，以获得优异的非对映选择性，即0℃下反应得到的(2'S)-或(2'R)-2'-脱氧-[2'-2H]核糖核苷的非对映选择性与使用Bu3SnH或Bu3Sn2H-Et3B体系在<-70℃下反应得到的非对映选择性相当；通过(Me3Si)3Si2H-Et3B体系在0℃下对2'-O-苯氧基硫代羰基-3',5'-O-TIPDS-核糖核苷进行还原氘代反应，也得到了具有上述高非对映选择性的(2'R)-2'-脱氧[2'-2H]核糖核苷。
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