(2S,3S,4S,5S,6R,9S,11S)-9-ethyl-3,5,11-trimethyl-2-[(2S,3S)-3-methyl-6-(1-phenyltetrazol-5-yl)sulfanyl-2-triethylsilyloxyhexyl]-4-triethylsilyloxy-1-oxa-7-azaspiro[5.5]undecan-8-one | 256326-88-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (2S,3S,4S,5S,6R,9S,11S)-9-ethyl-3,5,11-trimethyl-2-[(2S,3S)-3-methyl-6-(1-phenyltetrazol-5-yl)sulfanyl-2-triethylsilyloxyhexyl]-4-triethylsilyloxy-1-oxa-7-azaspiro[5.5]undecan-8-one
• CAS: 256326-88-2
• 化学式: C₄₀H₇₁N₅O₄SSi₂
• 分子量: 774.272
• InChiKey: RARIZWBPCDANSI-PDRRCDFNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.89
• 重原子数：
  52
• 可旋转键数：
  20
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  126
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2S,3S,4S,5S,6R,9S,11S)-9-ethyl-3,5,11-trimethyl-2-[(2S,3S)-3-methyl-6-(1-phenyltetrazol-5-yl)sulfanyl-2-triethylsilyloxyhexyl]-4-triethylsilyloxy-1-oxa-7-azaspiro[5.5]undecan-8-one 在 sodium periodate 、 四氧化锇 、 Hydroquinone 1,4-phthalazinediyl diether 、 甲基磺酰胺 、 四丁基氟化铵 、 硼酸 、 sodium hexamethyldisilazane 、 碳酸氢钠 、 potassium carbonate 、 对甲苯磺酸 、 间氯过氧苯甲酸 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 102.0h， 生成 (2S,3R,4S,5S,6R,9S,11S)-9-ethyl-4-hydroxy-2-(((2S,3S)-6-hydroxy-3-methyltetrahydro-2H-pyran-2-yl)methyl)-3,5,11-trimethyl-1-oxa-7-azaspiro[5.5]undecan-8-one
  参考文献：
  名称：

  Toward a Total Synthesis of the Immunosuppressant Sanglifehrin A. Preparation of Two Relay Compounds by Degradation and Their Use in the Reassembly of the Natural Product

  摘要：

  A potential relay route for the synthesis of the novel immunosuppressive agent sanglifehrin A (1) has been developed. Degradation of 1 by a sequence involving regioselective dihydroxylation of the C26,C27 double bond, followed by periodate cleavage of the resulting diol 4, afforded lactol 2 and macrocyclic aldehyde 3. Intramolecular ketal formation between the 1,3-diol and ketone functions present in 3 gave ketal-aldehyde 5. Lactol 2 was converted into sulfone 14 in four steps. The fragments 5 and 14 were reassembled, using the Julia-Kocienski olefination procedure, to afford intermediate 15, which was converted back to sanglifehrin A (1) after two deprotection steps.

  DOI：

  10.1021/jo9912395
• 作为产物：
  描述：

  三乙基硅基三氟甲磺酸酯 、 (2S,3R,4S,5S,6R,9S,11S)-9-ethyl-4-hydroxy-2-[(2S,3S)-2-hydroxy-3-methyl-6-(1-phenyltetrazol-5-yl)sulfanylhexyl]-3,5,11-trimethyl-1-oxa-7-azaspiro[5.5]undecan-8-one 在 吡啶 作用下， 以 乙腈 为溶剂， 反应 0.5h， 以72%的产率得到(2S,3S,4S,5S,6R,9S,11S)-9-ethyl-3,5,11-trimethyl-2-[(2S,3S)-3-methyl-6-(1-phenyltetrazol-5-yl)sulfanyl-2-triethylsilyloxyhexyl]-4-triethylsilyloxy-1-oxa-7-azaspiro[5.5]undecan-8-one
  参考文献：
  名称：

  Toward a Total Synthesis of the Immunosuppressant Sanglifehrin A. Preparation of Two Relay Compounds by Degradation and Their Use in the Reassembly of the Natural Product

  摘要：

  A potential relay route for the synthesis of the novel immunosuppressive agent sanglifehrin A (1) has been developed. Degradation of 1 by a sequence involving regioselective dihydroxylation of the C26,C27 double bond, followed by periodate cleavage of the resulting diol 4, afforded lactol 2 and macrocyclic aldehyde 3. Intramolecular ketal formation between the 1,3-diol and ketone functions present in 3 gave ketal-aldehyde 5. Lactol 2 was converted into sulfone 14 in four steps. The fragments 5 and 14 were reassembled, using the Julia-Kocienski olefination procedure, to afford intermediate 15, which was converted back to sanglifehrin A (1) after two deprotection steps.

  DOI：

  10.1021/jo9912395

文献信息

• Toward a Total Synthesis of the Immunosuppressant Sanglifehrin A. Preparation of Two Relay Compounds by Degradation and Their Use in the Reassembly of the Natural Product
  作者：Rainer Metternich、Donatienne Denni、Binh Thai、Richard Sedrani

  DOI：10.1021/jo9912395

  日期：1999.12.1

  A potential relay route for the synthesis of the novel immunosuppressive agent sanglifehrin A (1) has been developed. Degradation of 1 by a sequence involving regioselective dihydroxylation of the C26,C27 double bond, followed by periodate cleavage of the resulting diol 4, afforded lactol 2 and macrocyclic aldehyde 3. Intramolecular ketal formation between the 1,3-diol and ketone functions present in 3 gave ketal-aldehyde 5. Lactol 2 was converted into sulfone 14 in four steps. The fragments 5 and 14 were reassembled, using the Julia-Kocienski olefination procedure, to afford intermediate 15, which was converted back to sanglifehrin A (1) after two deprotection steps.