2-[(1R,2R,3R,5S)-5-[tert-butyl(dimethyl)silyl]oxy-3-(oxan-2-yloxy)-2-[(E,3R)-3-(oxan-2-yloxy)-4-phenoxybut-1-enyl]cyclopentyl]acetaldehyde | 99612-16-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-[(1R,2R,3R,5S)-5-[tert-butyl(dimethyl)silyl]oxy-3-(oxan-2-yloxy)-2-[(E,3R)-3-(oxan-2-yloxy)-4-phenoxybut-1-enyl]cyclopentyl]acetaldehyde
• CAS: 99612-16-5
• 化学式: C₃₃H₅₂O₇Si
• 分子量: 588.857
• InChiKey: LAPAKEAVSGFTMS-FPAUKCNWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.06
• 重原子数：
  41
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-[(1R,2R,3R,5S)-5-[tert-butyl(dimethyl)silyl]oxy-3-(oxan-2-yloxy)-2-[(E,3R)-3-(oxan-2-yloxy)-4-phenoxybut-1-enyl]cyclopentyl]acetaldehyde 在 吡啶 、 四溴化碳 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (3S)-3-Bromo-4-<(1R,2R,3R,5S)-5-<(tert-butyldimethylsilyl)oxy>-2-<(E)-(3R)-4-phenoxy-3-<(tetrahydro-2H-pyran-2-yl)oxy>-1-butenyl>-3-<(tetrahydro-2H-pyran-2-yl)oxy>cyclopentyl>but-1-yne
  参考文献：
  名称：

  Synthesis of the four stereoisomers of enprostil

  摘要：

  The four stereoisomeric components of enprostil (1a-d) were prepared using an orthoester Claisen rearrangement of individual propargylic alcohol intermediates 8 to generate the required allene upper chain stereochemistry, followed by one-carbon homologation. All four of the key propargylic alcohols 8 were prepared by addition of ethynyl Grignard reagent to aldehyde 7 (and to its enantiomer) and chromatographic separation of the diastereomers. Isomer 8a was also prepared by asymmetric reduction of propargylic ketone 10, which was in turn efficiently prepared by the opening of lactone 3 with dichlorocerium acetylide followed by silylation. Propargylic alcohol 8a was stereospecifically converted to enprostil isomer 1a via reaction of the inverted propargylic bromide 21 with the three-carbon functionalized organocuprate 22, easily prepared from methyl 3-bromopropionate.

  DOI：

  10.1021/jo00068a023
• 作为产物：
  描述：

  (3aR,4R,5R,6aS)-Hexahydro-4-<(E)-(3R)-4-phenoxy-3-<(tetrahydro-2H-pyran-2-yl)oxy>-1-butenyl>-5-<(tetrahydro-2H-pyran-2-yl)oxy>-2H-cyclopentafuran-2-one 在 吡啶 、 咪唑 、 chromium(VI) oxide 、 氢氧化钾 、 Celite 、 二异丁基氢化铝 、 碳酸氢钠 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 28.5h， 生成 2-[(1R,2R,3R,5S)-5-[tert-butyl(dimethyl)silyl]oxy-3-(oxan-2-yloxy)-2-[(E,3R)-3-(oxan-2-yloxy)-4-phenoxybut-1-enyl]cyclopentyl]acetaldehyde
  参考文献：
  名称：

  Synthesis of the four stereoisomers of enprostil

  摘要：

  The four stereoisomeric components of enprostil (1a-d) were prepared using an orthoester Claisen rearrangement of individual propargylic alcohol intermediates 8 to generate the required allene upper chain stereochemistry, followed by one-carbon homologation. All four of the key propargylic alcohols 8 were prepared by addition of ethynyl Grignard reagent to aldehyde 7 (and to its enantiomer) and chromatographic separation of the diastereomers. Isomer 8a was also prepared by asymmetric reduction of propargylic ketone 10, which was in turn efficiently prepared by the opening of lactone 3 with dichlorocerium acetylide followed by silylation. Propargylic alcohol 8a was stereospecifically converted to enprostil isomer 1a via reaction of the inverted propargylic bromide 21 with the three-carbon functionalized organocuprate 22, easily prepared from methyl 3-bromopropionate.

  DOI：

  10.1021/jo00068a023

文献信息

• Synthesis of the four stereoisomers of enprostil
  作者：Gary F. Cooper、Douglas L. Wren、David Y. Jackson、Colin C. Beard、Edvige Galeazzi、Albert R. Van Horn、Tsung T. Li

  DOI：10.1021/jo00068a023

  日期：1993.7

  The four stereoisomeric components of enprostil (1a-d) were prepared using an orthoester Claisen rearrangement of individual propargylic alcohol intermediates 8 to generate the required allene upper chain stereochemistry, followed by one-carbon homologation. All four of the key propargylic alcohols 8 were prepared by addition of ethynyl Grignard reagent to aldehyde 7 (and to its enantiomer) and chromatographic separation of the diastereomers. Isomer 8a was also prepared by asymmetric reduction of propargylic ketone 10, which was in turn efficiently prepared by the opening of lactone 3 with dichlorocerium acetylide followed by silylation. Propargylic alcohol 8a was stereospecifically converted to enprostil isomer 1a via reaction of the inverted propargylic bromide 21 with the three-carbon functionalized organocuprate 22, easily prepared from methyl 3-bromopropionate.