(3aR,4S,5R,6aS)-5-((tert-butyldiphenylsilyl)oxy)-4-(hydroxymethyl)hexahydro-2H-cyclopenta[b]furan-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3aR,4S,5R,6aS)-5-((tert-butyldiphenylsilyl)oxy)-4-(hydroxymethyl)hexahydro-2H-cyclopenta[b]furan-2-one
• 英文别名: (3aR,4S,5R,6aS)-5-[tert-butyl(diphenyl)silyl]oxy-4-(hydroxymethyl)-3,3a,4,5,6,6a-hexahydrocyclopenta[b]furan-2-one
• 化学式: C₂₄H₃₀O₄Si
• 分子量: 410.585
• InChiKey: QELTYGJDIYMCFJ-YUMYIRISSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3aR,4S,5R,6aS)-5-((tert-butyldiphenylsilyl)oxy)-4-(hydroxymethyl)hexahydro-2H-cyclopenta[b]furan-2-one 在 platinum on carbon potassium tert-butylate 、 四丁基氟化铵 、 氢气 、 二异丁基氢化铝 、 caesium carbonate 、 三乙胺 、 (-)-diisopinocamphenylborane chloride 、 lithium chloride 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 45.42h， 生成 拉坦前列素
  参考文献：
  名称：

  Process for the synthesis of prostaglandins and intermediates thereof

  摘要：

  公开号：

  EP2495235B1
• 作为产物：
  描述：

  (1S,5R,6R,7R)-7-(tert-butyldiphenylsilyloxy)-6-vinyl-2-oxabicyclo[3.3.0]octan-3-one 在 臭氧 、 dimethyl sulfide borane 作用下， 以 二氯甲烷 为溶剂， 以74%的产率得到(3aR,4S,5R,6aS)-5-((tert-butyldiphenylsilyl)oxy)-4-(hydroxymethyl)hexahydro-2H-cyclopenta[b]furan-2-one
  参考文献：
  名称：

  A short multigram asymmetric synthesis of prostanoid scaffolds

  摘要：

  Enantiomerically pure polysubstituted cyclopentanes which can be regarded as prostanoid scaffolds have been prepared by an efficient synthetic sequence readily applicable to the preparation of multigram quantities. The first key reaction is the diastereoselective allylmetallation of oxoamide 4 which is readily prepared from gamma-butyrolactone and an enantiomerically pure 2,5-dimethylpyrrolidine. The second key-step is an intramolecular [2+2] cycloaddition of a keteneiminium salt leading to bicylo[3.2.0] heptanones. These intermediates have been easily transformed into a variety of prostanoid scaffolds of high enantionneric purities. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00920-7

文献信息

• Novel synthetic approach to alfaprostol key intermediates via Stille coupling with an alkyne
  作者：Sara Monteiro、Aleš Imramovský、Karel Pauk、Jan Pavlík

  DOI：10.1016/j.tetlet.2017.04.091

  日期：2017.6

  Novel intermediates based on the Corey skeleton for preparation of the ω-chain of non-halogenated unnatural prostaglandin analogues containing a triple bond at position 13–14 (PG numbering) were synthesized. The utilization of a novel synthetic approach towards a new tin intermediate, and subsequent Stille coupling opens up new possibilities for preparing these important pharmaceutical intermediates

  合成了基于Corey骨架的新型中间体，该中间体可用于制备非卤代非天然前列腺素类似物的ω链，该类似物在13–14位具有三键（PG编号）。将新颖的合成方法用于新的锡中间体，以及随后的Stille偶联，为制备这些重要的药物中间体开辟了新的可能性。
• A Novel Chemoselective Cleavage of (<i>tert</i>-Butyl)(dimethyl)silyl (TBS) Ethers Catalyzed by Ce(SO₄)₂⋅4 H₂O
  作者：Davir González-Calderón、Carlos A. González-González、Aydeé Fuentes-Benítez、Erick Cuevas-Yáñez、David Corona-Becerril、Carlos González-Romero

  DOI：10.1002/hlca.201300354

  日期：2014.7

  (tert‐Butyl)(dimethyl)silyl (tBuMe2Si; TBS) phenyl/alkyl ethers were efficiently cleaved to the corresponding parent hydroxy compounds in good yields using catalytic amounts of Ce(SO4)2⋅4 H2O by microwave‐assisted or conventional heating in MeOH. Intramolecular and competitive experiments demonstrated the chemoselective deprotection of TBS ethers in the presence of triisopropylsilyl (iPr3Si; TIPS)

  （叔丁基）（二甲基）甲硅烷基（吨BuMe 2的Si; TBS）苯基/烷基醚得到有效切割而以良好的收率使用催化量的Ce的相应的亲本羟基化合物（SO 4）2 ⋅4ħ 2 ö通过微波辅助或常规在MeOH中加热。分子内和竞争实验表明，在三异丙基甲硅烷基（i Pr 3 Si; TIPS）和（叔丁基）（二苯基）甲硅烷基（t BuPh 2 Si; TBDPS）醚存在下，TBS醚的化学选择性脱保护。
• Aluminium Chloride Hexahydrate (AlCl₃ · 6H₂O): An Efficient, Facile, Mild, And Highly Chemoselective Catalytic Deprotection of Tert-Butyldimethylsilyl (TBS) Ethers
  作者：Davir González-Calderón、Luis J. Benitez-Puebla、Carlos A. Gonzalez-Gonzalez、Marco A. Garcia-Eleno、Aydeé Fuentes-Benitez、Erick Cuevas-Yañez、David Corona-Becerril、Carlos González-Romero

  DOI：10.1080/00397911.2013.851243

  日期：2014.5.3

  Abstract tert-Butyldimethylsilyl (TBS) phenyl / alkyl ethers were cleaved to the corresponding efficiently parent hydroxyl compounds in good yields using catalytic amounts of AlCl3 · 6H2O by conventional or microwave-assisted heating in methanol or isopropanol solution. Intramolecular and competitive experiments demonstrated the chemoselective deprotection of TBS ethers in the presence of triisopropylsilyl

  摘要 使用催化量的 AlCl3·6H2O 通过常规或微波辅助加热在甲醇或异丙醇溶液中，叔丁基二甲基甲硅烷基 (TBS) 苯基/烷基醚以良好的产率裂解为相应的有效母体羟基化合物。分子内和竞争实验证明了在三异丙基甲硅烷基和叔丁基二苯基甲硅烷基醚存在下 TBS 醚的化学选择性脱保护。图形概要
• Process for the synthesis of prostaglandins and intermediates thereof
  申请人：Newchem S.p.A.

  公开号：EP2495235B1

  公开（公告）日：2015-08-05
• A short multigram asymmetric synthesis of prostanoid scaffolds
  作者：Dominique Depré、Lian-Yong Chen、Léon Ghosez

  DOI：10.1016/s0040-4020(03)00920-7

  日期：2003.8

  Enantiomerically pure polysubstituted cyclopentanes which can be regarded as prostanoid scaffolds have been prepared by an efficient synthetic sequence readily applicable to the preparation of multigram quantities. The first key reaction is the diastereoselective allylmetallation of oxoamide 4 which is readily prepared from gamma-butyrolactone and an enantiomerically pure 2,5-dimethylpyrrolidine. The second key-step is an intramolecular [2+2] cycloaddition of a keteneiminium salt leading to bicylo[3.2.0] heptanones. These intermediates have been easily transformed into a variety of prostanoid scaffolds of high enantionneric purities. (C) 2003 Elsevier Ltd. All rights reserved.