N³-benzoyl-3',5'-O-(di-tert-butylsilanediyl)-2'-O-benzyluridine

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N³-benzoyl-3',5'-O-(di-tert-butylsilanediyl)-2'-O-benzyluridine
• 英文别名: N3-benzoyl-2'-O-benzyl-3',5'-O-(di-tert-butylsilanediyl)uridine；1-[(4aR,6R,7R,7aR)-2,2-ditert-butyl-7-phenylmethoxy-4a,6,7,7a-tetrahydro-4H-furo[3,2-d][1,3,2]dioxasilin-6-yl]-3-benzoylpyrimidine-2,4-dione
• 化学式: C₃₁H₃₈N₂O₇Si
• 分子量: 578.737
• InChiKey: YAZMHDSLFBKCNQ-GTVIQNQPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  41
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  94.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  二叔丁基硅基双(三氟甲烷磺酸) 在 三乙基硅烷 、 三氟甲磺酸三甲基硅酯 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.67h， 生成 N³-benzoyl-3',5'-O-(di-tert-butylsilanediyl)-2'-O-benzyluridine
  参考文献：
  名称：

  Trimethylsilyl Trifluoromethanesulfonate-promoted Reductive 2′-O-arylmethylation of Ribonucleoside Derivatives

  摘要：

  Arylmethyl groups such as benzyl, p-methoxybenzyl, and 1-pyrenylmethyl groups were introduced to the 2'-O-position of nucleosides by reductive etherification. Combining corresponding aromatic aldehydes with 2'-O-trimethylsilylnucleoside derivatives in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) resulted in moderate to good yields of the 2'-O-arylmethyluridine derivatives, whereas the corresponding cytidine and adenosine derivatives were obtained in low yields. The reaction of ribonucleosides with aliphatic aldehydes did not proceed smoothly. Anomerization of the uridine derivatives by TMSOTf was observed in CH(2)Cl(2), toluene, and CH(3)CN, but was completely suppressed when the reactions were conducted in 1,4-dioxane.

  DOI：

  10.1080/15257770.2011.592171

文献信息

• REACTION OF N³-BENZOYL-3′,5′-<i>O</i>-(DI-<i>TERT</i>-BUTYLSILANEDIYL)URIDINE WITH HINDERED ELECTROPHILES: INTERMOLECULAR N³To 2′-<i>O</i>PROTECTING GROUP TRANSFER
  作者：Lei Zhu、Osvaldo dos Santos、Nadrian C. Seeman、James W. Canary

  DOI：10.1081/ncn-120015728

  日期：2002.12

  alkylated with various alkyl iodides in CH3CN in the presence of base. Normal 2'-O-alkylated products were obtained with methyl or benzyl iodide. If hindered alkyl iodides with beta-branching such as 2-ethylbutyl iodide were used as electrophiles under the same conditions, N3-alkyl-2'-O-benzoyl uridine derivatives were produced. This unexpected transformation is usually dormant with reactive alkylating agents

  在碱存在下，在CH 3 CN中用各种烷基碘将化合物N3-苯甲酰基-3'，5'-O-（二叔丁基硅烷二基）尿苷2烷基化。用甲基或苄基碘获得正常的2'-O-烷基化产物。如果在相同条件下将具有β-支链的受阻烷基碘化物（例如2-乙基丁基碘化物）用作亲电试剂，则可制得N3-烷基-2'-O-苯甲酰尿苷衍生物。这种出乎意料的转变通常在反应性烷基化剂中处于休眠状态，但在空间位阻，反应性较低的亲电子试剂中表达。这种不需要的反应会产生异构体产物，其光谱与目标化合物的光谱仅细微差别。
• Trimethylsilyl Trifluoromethanesulfonate-promoted Reductive 2′-<i>O</i>-arylmethylation of Ribonucleoside Derivatives
  作者：Naoki Uchiyama、Toshihiko Ogata、Natsuhisa Oka、Takeshi Wada

  DOI：10.1080/15257770.2011.592171

  日期：2011.6.1

  Arylmethyl groups such as benzyl, p-methoxybenzyl, and 1-pyrenylmethyl groups were introduced to the 2'-O-position of nucleosides by reductive etherification. Combining corresponding aromatic aldehydes with 2'-O-trimethylsilylnucleoside derivatives in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) resulted in moderate to good yields of the 2'-O-arylmethyluridine derivatives, whereas the corresponding cytidine and adenosine derivatives were obtained in low yields. The reaction of ribonucleosides with aliphatic aldehydes did not proceed smoothly. Anomerization of the uridine derivatives by TMSOTf was observed in CH(2)Cl(2), toluene, and CH(3)CN, but was completely suppressed when the reactions were conducted in 1,4-dioxane.