(2S,3R,4S,5S,6R,9S,11S)-2-[(2S,3S)-2,6-dihydroxy-3-methylhexyl]-9-ethyl-4-hydroxy-3,5,11-trimethyl-1-oxa-7-azaspiro[5.5]undecan-8-one | 256326-86-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂螺癸烷衍生物
• 英文名称: (2S,3R,4S,5S,6R,9S,11S)-2-[(2S,3S)-2,6-dihydroxy-3-methylhexyl]-9-ethyl-4-hydroxy-3,5,11-trimethyl-1-oxa-7-azaspiro[5.5]undecan-8-one
• CAS: 256326-86-0
• 化学式: C₂₁H₃₉NO₅
• 分子量: 385.544
• InChiKey: KFXWMHVCUVNRPZ-FIFITYNBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  99
• 氢给体数：
  4
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-苯基-5-巯基四氮唑 、 (2S,3R,4S,5S,6R,9S,11S)-2-[(2S,3S)-2,6-dihydroxy-3-methylhexyl]-9-ethyl-4-hydroxy-3,5,11-trimethyl-1-oxa-7-azaspiro[5.5]undecan-8-one 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 30.0h， 以71%的产率得到(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
  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：

  (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 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以93%的产率得到(2S,3R,4S,5S,6R,9S,11S)-2-[(2S,3S)-2,6-dihydroxy-3-methylhexyl]-9-ethyl-4-hydroxy-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

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.