Germyldesulfonylation反应在含锗核苷类似物合成中的应用。
Application of germyldesulfonylation reactions to the synthesis of germanium-containing nucleoside analogues.
作者信息
Wnuk Stanislaw F, Sacasa Pablo R, Restrepo Jorge
机构信息
Department of Chemistry & Biochemistry, Florida International University, Miami, Florida, USA.
出版信息
Nucleosides Nucleotides Nucleic Acids. 2009 May;28(5):537-49. doi: 10.1080/15257770903054340.
Treatment of the protected (E)-5'-deoxy-5'-[(p-toluenesulfonyl)methylene]uridine and adenosine derivatives with tributyl- or triphenylgermane hydride (AIBN/toluene/Delta) effected radical-mediated germyldesulfonylations to give 5'-(tributyl- or triphenylgermyl)methylene-5'-deoxyuridine and adenosine derivatives as single (E)-isomers. Analogous treatment of 2'-deoxy-2'-[(phenylsulfonyl)methylene]uridine with Ph(3)GeH afforded the corresponding vinyl triphenylgermane product. Stereoselective halodegermylation of the (E)-5'-(tributylgermyl)methylene-5'-deoxy nucleosides with N-iodosuccinimide or N-bromosuccinimide provided the Wittig-type (E)-5'-deoxy-5'-(halomethylene) nucleosides quantitatively, while no halodegermylations was observed with the 5'-deoxy-5'-(triphenylgermyl)methylene counterparts. Treatment of the vinyl trialkylgermanes with aqueous trifluoroacetic acid effected protiodegermylation, while vinyl triarylgermanes were stable under the acidic conditions.
用三丁基或三苯基锗烷氢化物（偶氮二异丁腈/甲苯/加热）处理受保护的（E）-5'-脱氧-5'-[(对甲苯磺酰基)亚甲基]尿苷和腺苷衍生物，可实现自由基介导的脱磺酰锗化反应，得到5'-（三丁基或三苯基锗基）亚甲基-5'-脱氧尿苷和腺苷衍生物，为单一的（E）-异构体。用三苯基锗烷氢化物（Ph(3)GeH）对2'-脱氧-2'-[(苯基磺酰基)亚甲基]尿苷进行类似处理，得到相应的乙烯基三苯基锗产物。用N-碘代琥珀酰亚胺或N-溴代琥珀酰亚胺对（E）-5'-（三丁基锗基）亚甲基-5'-脱氧核苷进行立体选择性卤代脱锗反应，可定量得到维蒂希型（E）-5'-脱氧-5'-（卤代亚甲基）核苷，而5'-脱氧-5'-（三苯基锗基）亚甲基类似物则未观察到卤代脱锗反应。用三氟乙酸水溶液处理乙烯基三烷基锗可实现质子脱锗反应，而乙烯基三芳基锗在酸性条件下稳定。
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