(3aR,6S,6aS)-6-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-3a,5,6,6a-tetrahydrocyclopenta[d][1,3]dioxol-4-one | 273381-26-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,6S,6aS)-6-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-3a,5,6,6a-tetrahydrocyclopenta[d][1,3]dioxol-4-one
• CAS: 273381-26-3
• 化学式: C₁₄H₂₆O₄Si
• 分子量: 286.444
• InChiKey: KXGMFTLLBZTKAO-SDDRHHMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3aR,6S,6aS)-6-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-3a,5,6,6a-tetrahydrocyclopenta[d][1,3]dioxol-4-one 在 cerium(III) chloride 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 (3aR,4S,6S,6aR)-2,2,4-trimethyl-3a,5,6,6a-tetrahydrocyclopenta[d][1,3]dioxole-4,6-diol
  参考文献：
  名称：

  利用具有潜在内消旋结构的手性环戊烯醇的对映异构途径合成α-cuparenone

  摘要：

  利用具有潜在内消旋结构的手性环戊烷类原料，已经开发出一种有效的对映发散途径，以两种对映体形式分离出的倍半萜烯-α-cuparenone 。

  DOI：

  10.1016/s0040-4039(00)00235-5
• 作为产物：
  描述：

  tert-Butyl-dimethyl-[(1S,4R)-4-(1-methyl-1-phenyl-ethoxy)-cyclopent-2-enyloxy]-silane 在 palladium on activated charcoal 、 四氧化锇 、 氯仿 、 4-甲基苯磺酸吡啶 N-甲基吲哚酮 、 氢气 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 生成 (3aR,6S,6aS)-6-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-3a,5,6,6a-tetrahydrocyclopenta[d][1,3]dioxol-4-one
  参考文献：
  名称：

  利用具有潜在内消旋结构的手性环戊烯醇的对映异构途径合成α-cuparenone

  摘要：

  利用具有潜在内消旋结构的手性环戊烷类原料，已经开发出一种有效的对映发散途径，以两种对映体形式分离出的倍半萜烯-α-cuparenone 。

  DOI：

  10.1016/s0040-4039(00)00235-5

文献信息

• Chiral Preparation of Polyoxygenated Cyclopentanoids
  作者：Hiromi Nakashima、Masayuki Sato、Takahiko Taniguchi、Kunio Ogasawara

  DOI：10.1055/s-2000-6271

  日期：——

  A series of polyoxygenated cyclopentanoids, including 2,2-dimethyl-3a,6a-dihydro-4H-cyclopenta[d][1,3]dioxol-4-one, has been prepared in both enantiomeric forms from cyclopentadiene by employing lipase-mediated kinetic resolution as the key step. Thus, cyclopentadiene is first transformed into racemic cis-4-cumyloxycyclopent-2-en-1-ol which is resolved under transesterification conditions in the presence of lipase PS. After transformation into the corresponding tert-butyldimethylsilyl (TBS) ethers, each of the enantiomers is cis-dihydroxylated diastereoselectively from the less hindered face which is transformed into the 2,3-O-isopropylidene-1,4-di-O-protected (trans-1,2 : cis-2,3 : trans-3,4)-1,2,3,4-cyclopentanetetraol. Selective removal of the 1,4-protecting group gives the corresponding 2,3,4-O-protected cyclopentanols which are further transformed into the 2,3,4-O-protected cyclopentanones on oxidation without suffering β-elimination. Exposure of the cyclopentanones to warm acetic acid allows β-elimination to give rise to the dehydration product 2,2-dimethyl-3a,6a-dihydro-4H-cyclopenta[d][1,3]dioxol-4-one having the corresponding chirality without losing their original chiral integrity.

  一系列多氧化环戊烷类化合物，包括2,2-二甲基-3a,6a-二氢-4H-环戊烯基[d][1,3]二氧杂环-4-酮，已通过使用脂肪酶介导的动力学分离从环戊二烯中制备成两种对映异构体。因此，环戊二烯首先转化为外消旋cis-4-香草基氧环戊-2-烯-1-醇，该化合物在脂肪酶PS的存在下在转酯化条件下被分离。经过转化成相应的叔丁基二甲基硅基（TBS）醚后，每个对映体都从较少阻碍的面选择性地进行cis-二羟基化，转化为2,3-O-异丙缩酮-1,4-二-O-保护的（trans-1,2 : cis-2,3 : trans-3,4）-1,2,3,4-环戊烷四醇。选择性去除1,4-保护基团得到相应的2,3,4-O-保护环戊醇，这些化合物在氧化过程中进一步转化为2,3,4-O-保护的环戊酮而不发生β-消除。将环戊酮暴露在温热的醋酸中，可以使β-消除反应发生，从而得到脱水产物2,2-二甲基-3a,6a-二氢-4H-环戊烯基[d][1,3]二氧杂环-4-酮，具有相应的手性且不失去其原有的手性完整性。
• A new synthesis and an antiviral assessment of the 4′-fluoro derivative of 4′-deoxy-5′-noraristeromycin
  作者：Xue-qiang Yin、Wei-kuan Li、Minmin Yang、Stewart W. Schneller

  DOI：10.1016/j.bmc.2009.03.004

  日期：2009.4

  A synthetic route to (1S, 2S, 3R, 5S)-3-(6-amino-9H-purin-9-yl)-5-fluorocyclopentane-1,2-diol (that is, the 4'-fluoro derivative of 4'-deoxy-5'-noraristeromycin, 3) is described via a fluorinated cyclopentanol, which is in contrast to existing schemes where fluorination occurred once the purine ring was present. Compound 3 was assayed versus a number of viruses. A favorable response was observed towards measles (IC50 of 1.2 mu g/mL in the neutral red assay and 14 mu g/mL by the visual assay) but this was accompanied by cytotoxicity in the CV-1 host cells (21-36 mu g/mL). Among the viruses unaffected by 3 were human cytomegalovirus and the poxviruses (vaccinia and cowpox), which are three viruses that were inhibited by the 40,40-difluoro analog of 3 (that is, 2). (C) 2009 Elsevier Ltd. All rights reserved.