(1R,4S,5S)-4-(tert-Butyl-dimethyl-silanyloxy)-bicyclo[3.2.0]hept-6-en-2-one

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1R,4S,5S)-4-(tert-Butyl-dimethyl-silanyloxy)-bicyclo[3.2.0]hept-6-en-2-one
• 英文别名: (1R,4S,5S)-4-[tert-butyl(dimethyl)silyl]oxybicyclo[3.2.0]hept-6-en-2-one
• 化学式: C₁₃H₂₂O₂Si
• 分子量: 238.402
• InChiKey: CDTDBIRONPPMBR-SCVCMEIPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4S,5S)-4-(tert-Butyl-dimethyl-silanyloxy)-bicyclo[3.2.0]hept-6-en-2-one 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 (R)-2-methyl-CBS-oxazoborolidine 、 (S)-2-甲基-CBS-恶唑硼烷 、 (R)-2-甲基-CBS-恶唑硼烷 4-二甲氨基吡啶 、 二异丁基氢化铝 、 三乙胺 、 pyridinium chlorochromate 、 儿萘酚硼烷 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 132.5h， 生成 (E)-(S)-1-[(1R,2S,3S,5R)-3,5-Bis-(tert-butyl-dimethyl-silanyloxy)-2-vinyl-cyclopentyl]-oct-1-en-3-ol
  参考文献：
  名称：

  Stereodivergent Synthesis of All 15-F₂ Isoprostanes

  摘要：

  Isoprostanes, lipid metabolites generated from free radical oxidation of membrane-bound arachidonic acid, have been detected in organisms subjected to oxidative stress; however, the function and cellular targets of the isoprostanes are unclear. As an initial step toward studying the biological role of these molecules, we report the preparation of all known and anticipated 15-F2 isoprostanes. The stereodivergent strategy to the complete isoprostane library features a ring-opening metathesis to introduce the cis-alkyl side chains that are characteristic of this class of molecules. Resolution to the individual stereoisomers can be accomplished by either a catalytic asymmetric reduction or an auxiliary-based separation protocol. In either case, the individual isomers can be converted to the corresponding 15-F2 isoprostanes through a straightforward functionalization of the carboxylic acid-containing side chain. The availability of this complete 15-F2 isoprostane library, containing both known and anticipated lipid metabolites, allows for the first time the side-by-side evaluation of these compounds in a variety of biological assays.

  DOI：

  10.1021/ja027154u
• 作为产物：
  描述：

  (1R,2S,4S,5S)-4-(tert-Butyl-dimethyl-silanyloxy)-bicyclo[3.2.0]hept-6-en-2-ol 在 aluminum oxide 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以756 mg的产率得到(1R,4S,5S)-4-(tert-Butyl-dimethyl-silanyloxy)-bicyclo[3.2.0]hept-6-en-2-one
  参考文献：
  名称：

  Stereodivergent Synthesis of All 15-F₂ Isoprostanes

  摘要：

  Isoprostanes, lipid metabolites generated from free radical oxidation of membrane-bound arachidonic acid, have been detected in organisms subjected to oxidative stress; however, the function and cellular targets of the isoprostanes are unclear. As an initial step toward studying the biological role of these molecules, we report the preparation of all known and anticipated 15-F2 isoprostanes. The stereodivergent strategy to the complete isoprostane library features a ring-opening metathesis to introduce the cis-alkyl side chains that are characteristic of this class of molecules. Resolution to the individual stereoisomers can be accomplished by either a catalytic asymmetric reduction or an auxiliary-based separation protocol. In either case, the individual isomers can be converted to the corresponding 15-F2 isoprostanes through a straightforward functionalization of the carboxylic acid-containing side chain. The availability of this complete 15-F2 isoprostane library, containing both known and anticipated lipid metabolites, allows for the first time the side-by-side evaluation of these compounds in a variety of biological assays.

  DOI：

  10.1021/ja027154u

文献信息

• Synthesis of Functionalized Bicyclo[3.2.0]heptanes - a Study of the [2+2] Photocycloaddition Reactions of 4-Hydroxycyclopent-2-enone Derivatives
  作者：Matthieu Le Liepvre、Jean Ollivier、David J. Aitken

  DOI：10.1002/ejoc.200900749

  日期：2009.12

  A selection of 4-hydroxycyclopent-2-enone derivatives were prepared in enantiomerically pure form, and their photochemical [2+2] cycloaddition reactions with a variety of alkenes were studied, with a view to providing diversely functionalized bicyclo[3.2.0]heptanes. Intermolecular reactions provided the target structures in reasonable yields as a mixture of exo and endo adducts, in proportions which

  以对映体纯形式制备了一系列 4-羟基环戊-2-烯酮衍生物，并研究了它们与各种烯烃的光化学 [2+2] 环加成反应，以期提供多种功能化的双环 [3.2.0] 庚烷. 分子间反应以合理的产率提供目标结构，作为外加合物和内加合物的混合物，其比例作为反应物的空间体积或反应条件的函数变化很小。该系统适用于分子内反应，提供单一的立体化学纯产物，这是刚性、凹面、三氧化骨架的方便前体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Stereodivergent Synthesis of All 15-F₂ Isoprostanes
  作者：Thomas O. Schrader、Marc L. Snapper

  DOI：10.1021/ja027154u

  日期：2002.9.1

  Isoprostanes, lipid metabolites generated from free radical oxidation of membrane-bound arachidonic acid, have been detected in organisms subjected to oxidative stress; however, the function and cellular targets of the isoprostanes are unclear. As an initial step toward studying the biological role of these molecules, we report the preparation of all known and anticipated 15-F2 isoprostanes. The stereodivergent strategy to the complete isoprostane library features a ring-opening metathesis to introduce the cis-alkyl side chains that are characteristic of this class of molecules. Resolution to the individual stereoisomers can be accomplished by either a catalytic asymmetric reduction or an auxiliary-based separation protocol. In either case, the individual isomers can be converted to the corresponding 15-F2 isoprostanes through a straightforward functionalization of the carboxylic acid-containing side chain. The availability of this complete 15-F2 isoprostane library, containing both known and anticipated lipid metabolites, allows for the first time the side-by-side evaluation of these compounds in a variety of biological assays.