(1R,3R,5R,8S)-8-{[(tert-butyl)dimethylsilyl]oxy}-5-hydroxy-3-methoxy-2-oxabicyclo[3.3.0]octan-7-one | 258504-93-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,3R,5R,8S)-8-{[(tert-butyl)dimethylsilyl]oxy}-5-hydroxy-3-methoxy-2-oxabicyclo[3.3.0]octan-7-one
• 英文别名: (2R,3aR,6S,6aR)-6-[tert-butyl(dimethyl)silyl]oxy-3a-hydroxy-2-methoxy-3,4,6,6a-tetrahydro-2H-cyclopenta[b]furan-5-one
• CAS: 258504-93-7
• 化学式: C₁₄H₂₆O₅Si
• 分子量: 302.443
• InChiKey: WMSUFRJRKNBBNS-BYNQJWBRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.84
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  甲氧基胺盐酸盐 、 (1R,3R,5R,8S)-8-{[(tert-butyl)dimethylsilyl]oxy}-5-hydroxy-3-methoxy-2-oxabicyclo[3.3.0]octan-7-one 在 sodium acetate 作用下， 以 乙醇 、 水 为溶剂， 反应 0.33h， 生成 (1R,3R,5S,7Z,8R)-8-{[(tert-butyl)dimethylsilyl]oxy}-5-hydroxy-3-methoxy-2-oxabicyclo[3.3.0]octan-6-one O-methyloxime 、 (1R,3R,5S,7E,8R)-8-{[(tert-butyl)dimethylsilyl]oxy}-5-hydroxy-3-methoxy-2-oxabicyclo[3.3.0]octan-6-one O-methyloxime
  参考文献：
  名称：

  Nucleic-Acid Analogs with Restricted Conformational Flexibility in the Sugar-Phosphate Backbone (`Bicyclo-DNA'), Part 7, Synthesis and Properties of Oligodeoxynucleotides Containing [(3′S,5′S,6′R)-6′-Amino-2′-deoxy-3′,5′-ethano-β-D-ribofuranosyl]thymine (=(6′R)-6′-Amino-bicyclo-thymidine)

  摘要：

  We describe the synthesis of the acetamido- and trifluoroacetamido-functionalized bicyclo-thymidines 11 and 12, starting from the silyl enol ether 1, in 6 steps. These nucleosides were converted to the corresponding cyanoethyl phosphoramidite building blocks 16 and 17 and subsequently incorporated into the homothymidylate decamers 18-22. Upon deprotection of the oligomers, the trifluoroacetamido functions were cleaved, leaving behind a free amino function in the sugar-phosphate backbone that is protonated at neutral pH, giving rise to partially zwitterionic oligonucleotides. Pairing properties with the complementary DNA oligomer d(A(10)), as determined by UV/melting curves, revealed a slightly increased stability of the duplex d(A(10)) . 20, in which the decathymidylate sequence shows an alternating arrangement of natural thymidine and amino-bicyclo-thymidine residues, relative to the natural reference duplex. The dependence of T-m on the salt concentration of the medium is reduced in this case. Duplex destabilization occurs if the amino-bicyclo-thymidine residues are replaced by the charge-neutral acetamido-bicyclo-nucleosides (e.g., d(A(10)) . 22), most probably due to steric interference of the acetamido substituent with the backbone P-O(5') bond.

  DOI：

  10.1002/(sici)1522-2675(19991110)82:11<1813::aid-hlca1813>3.0.co;2-0
• 作为产物：
  描述：

  (1R,3R,5S,7S,8R)-8-{[(tert-butyl)dimethylsilyl]oxy}-3-methoxy-2-oxabicyclo[3.3.0]octan-5,7-diol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以740 mg的产率得到(1R,3R,5R,8S)-8-{[(tert-butyl)dimethylsilyl]oxy}-5-hydroxy-3-methoxy-2-oxabicyclo[3.3.0]octan-7-one
  参考文献：
  名称：

  Nucleic-Acid Analogs with Restricted Conformational Flexibility in the Sugar-Phosphate Backbone (`Bicyclo-DNA'), Part 7, Synthesis and Properties of Oligodeoxynucleotides Containing [(3′S,5′S,6′R)-6′-Amino-2′-deoxy-3′,5′-ethano-β-D-ribofuranosyl]thymine (=(6′R)-6′-Amino-bicyclo-thymidine)

  摘要：

  We describe the synthesis of the acetamido- and trifluoroacetamido-functionalized bicyclo-thymidines 11 and 12, starting from the silyl enol ether 1, in 6 steps. These nucleosides were converted to the corresponding cyanoethyl phosphoramidite building blocks 16 and 17 and subsequently incorporated into the homothymidylate decamers 18-22. Upon deprotection of the oligomers, the trifluoroacetamido functions were cleaved, leaving behind a free amino function in the sugar-phosphate backbone that is protonated at neutral pH, giving rise to partially zwitterionic oligonucleotides. Pairing properties with the complementary DNA oligomer d(A(10)), as determined by UV/melting curves, revealed a slightly increased stability of the duplex d(A(10)) . 20, in which the decathymidylate sequence shows an alternating arrangement of natural thymidine and amino-bicyclo-thymidine residues, relative to the natural reference duplex. The dependence of T-m on the salt concentration of the medium is reduced in this case. Duplex destabilization occurs if the amino-bicyclo-thymidine residues are replaced by the charge-neutral acetamido-bicyclo-nucleosides (e.g., d(A(10)) . 22), most probably due to steric interference of the acetamido substituent with the backbone P-O(5') bond.

  DOI：

  10.1002/(sici)1522-2675(19991110)82:11<1813::aid-hlca1813>3.0.co;2-0