Ethyl (4S,5S,6S)-8-azido-4,5-epoxy-6-hydroxy-(E)-2-octenoate | 151953-14-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Ethyl (4S,5S,6S)-8-azido-4,5-epoxy-6-hydroxy-(E)-2-octenoate
• 英文别名: ethyl (E)-3-[(2S,3S)-3-[(1S)-3-azido-1-hydroxypropyl]oxiran-2-yl]prop-2-enoate
• CAS: 151953-14-9
• 化学式: C₁₀H₁₅N₃O₄
• 分子量: 241.247
• InChiKey: FLMCIXUFHQSXHD-XFUCVFLYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  73.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Ethyl (4S,5S,6S)-8-azido-4,5-epoxy-6-hydroxy-(E)-2-octenoate 在 palladium on activated charcoal 吡啶 、 potassium osmate(VI) 、 (DHQ)2-PHAL 、 甲基磺酰胺 、 dimethyl sulfide borane 、 氢气 、 potassium carbonate 、 三氟乙酸 、 potassium hexacyanoferrate(III) 作用下， 以 乙醇 为溶剂， 反应 39.0h， 生成 栗精胺
  参考文献：
  名称：

  A concise, enantioselective synthesis of castanospermine

  摘要：

  A stereoselective synthesis of the polyhydroxy indolizidine alkaloids castanospermine (1) and 6,7-diepicastanospermine (4) has been achieved starting from the readily available alcohol 8. Subsequent Sharpless asymmetric epoxidation, followed by the azide displacement of the tosyl group gave the epoxy azide 12. The asymmetric dihydroxylation of 12 with (DHQ)2-PHAL gave the triol 13 in good diastereoselectivity. Alcohol protection, followed by reductive double cyclization of the resulting epoxy azide 17 gave 5-indolizidinone 18, which was then uneventfully converted to 1. On the other hand, the use of (DHQD)2-PHAL in the dihydroxylation of 12 provided a stereoselective preparation of 4.

  DOI：

  10.1021/jo00077a034
• 作为产物：
  描述：

  Ethyl (6S)-6-(triisopropylsiloxy)-8-<(p-toluenesulfonyl)oxy>-(E,E)-2,4-octadienoate 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 sodium azide 、 L-(+)-酒石酸二异丙酯 、 4 A molecular sieve 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 异辛烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.5h， 生成 Ethyl (4S,5S,6S)-8-azido-4,5-epoxy-6-hydroxy-(E)-2-octenoate
  参考文献：
  名称：

  A concise, enantioselective synthesis of castanospermine

  摘要：

  A stereoselective synthesis of the polyhydroxy indolizidine alkaloids castanospermine (1) and 6,7-diepicastanospermine (4) has been achieved starting from the readily available alcohol 8. Subsequent Sharpless asymmetric epoxidation, followed by the azide displacement of the tosyl group gave the epoxy azide 12. The asymmetric dihydroxylation of 12 with (DHQ)2-PHAL gave the triol 13 in good diastereoselectivity. Alcohol protection, followed by reductive double cyclization of the resulting epoxy azide 17 gave 5-indolizidinone 18, which was then uneventfully converted to 1. On the other hand, the use of (DHQD)2-PHAL in the dihydroxylation of 12 provided a stereoselective preparation of 4.

  DOI：

  10.1021/jo00077a034

文献信息

• A concise, enantioselective synthesis of castanospermine
  作者：No Soo Kim、Jong Ryoo Choi、Jin Kun Cha

  DOI：10.1021/jo00077a034

  日期：1993.12

  A stereoselective synthesis of the polyhydroxy indolizidine alkaloids castanospermine (1) and 6,7-diepicastanospermine (4) has been achieved starting from the readily available alcohol 8. Subsequent Sharpless asymmetric epoxidation, followed by the azide displacement of the tosyl group gave the epoxy azide 12. The asymmetric dihydroxylation of 12 with (DHQ)2-PHAL gave the triol 13 in good diastereoselectivity. Alcohol protection, followed by reductive double cyclization of the resulting epoxy azide 17 gave 5-indolizidinone 18, which was then uneventfully converted to 1. On the other hand, the use of (DHQD)2-PHAL in the dihydroxylation of 12 provided a stereoselective preparation of 4.