26(S),27(S)-dihydroxysanglifehrin A | 256424-82-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 26(S),27(S)-dihydroxysanglifehrin A
• 英文别名: (3S,6S,9R,10R,11S,12S,13E,15E,18S,21S)-18-[(E,4S,5S,8S,9S)-10-[(2S,3R,4S,5S,6R,9S,11S)-9-ethyl-4-hydroxy-3,5,11-trimethyl-8-oxo-1-oxa-7-azaspiro[5.5]undecan-2-yl]-4,5,9-trihydroxy-8-methyldec-2-en-2-yl]-10,12-dihydroxy-3-[(3-hydroxyphenyl)methyl]-11-methyl-9-(3-oxobutyl)-6-propan-2-yl-19-oxa-1,4,7,25-tetrazabicyclo[19.3.1]pentacosa-13,15-diene-2,5,8,20-tetrone
• CAS: 256424-82-5
• 化学式: C₆₀H₉₃N₅O₁₅
• 分子量: 1124.42
• InChiKey: KXNCVIBOXFGAFA-JIYAZNMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  80
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  314
• 氢给体数：
  11
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  26(S),27(S)-dihydroxysanglifehrin A 在 sodium tetrahydroborate 、 sodium periodate 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 3.0h， 生成 (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
• 作为产物：
  描述：

  sanglifehrin A 在 四氧化锇 、 Hydroquinone 1,4-phthalazinediyl diether 、 甲基磺酰胺 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 叔丁醇 为溶剂， 反应 2.0h， 以70%的产率得到26(S),27(S)-dihydroxysanglifehrin A
  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.