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-yn-3-one | 104023-66-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 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-yn-3-one
• 英文别名: 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-yn-3-one；1-[(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]but-3-yn-2-one
• CAS: 104023-66-7
• 化学式: C₃₅H₅₂O₇Si
• 分子量: 612.879
• InChiKey: WTAUVWZYSWMOEI-IYMVUKIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.06
• 重原子数：
  43.0
• 可旋转键数：
  13.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  72.45
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  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-yn-3-one 在 B-isopinocampheyl-9-borabicyclo[3.3.1]nonane 作用下， 反应 72.0h， 以90.1%的产率得到(3R)-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-yn-3-ol
  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：

  (3R/S)-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-yn-3-ol 在 3,5-二甲基吡唑 、 chromium(VI) oxide 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到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-yn-3-one
  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