首页> 美国卫生研究院文献>ACS Omega >Pyrimidine Nucleosides witha Reactive (β-Chlorovinyl)sulfoneor (β-Keto)sulfone Group at the C5 Position Their Reactionswith Nucleophiles and Electrophiles and Their Polymerase-CatalyzedIncorporation into DNA
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Pyrimidine Nucleosides witha Reactive (β-Chlorovinyl)sulfoneor (β-Keto)sulfone Group at the C5 Position Their Reactionswith Nucleophiles and Electrophiles and Their Polymerase-CatalyzedIncorporation into DNA

机译:嘧啶核苷与反应性(β-氯丁酰基)砜或在C5位的(β-酮)砜基团它们的反应亲核试剂和亲电试剂的聚合反应及其催化掺入DNA

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摘要

Transition-metal-catalyzed chlorosulfonylation of 5-ethynylpyrimidine nucleosides provided (E)-5-(β-chlorovinyl)sulfones >A, which undergo nucleophilic substitution with amines or thiols affording >B. The treatment of vinyl sulfones >A with ammonia followed by acid-catalyzed hydrolysis of the intermediary β-sulfonylvinylamines gave 5-(β-keto)sulfones >C. The latter reacts with electrophiles, yielding α-carbon-alkylated or -sulfanylated analogues >D. The 5′-triphosphates of >A and >C were incorporated into double-stranded DNA, using open and one-nucleotide gap substrates, by human or Escherichia coli DNA-polymerase-catalyzed reactions.
机译:过渡金属催化的5-乙炔基嘧啶核苷的氯磺酰化反应提供(E)-5-(β-氯乙烯基)砜> A ,该胺经过胺或硫醇的亲核取代,生成> B 。用氨处理乙烯基砜> A ,然后酸催化水解中间的β-磺酰基乙烯基胺,得到5-(β-酮基)砜> C 。后者与亲电试剂反应,生成α-碳-烷基化或-磺酰化类似物> D 。通过人或大肠杆菌DNA聚合酶催化,使用开放和单核苷酸缺口底物将> A 和> C 的5'-三磷酸酯掺入双链DNA中。反应。

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