1-acetyl-10-(tert-butyldiphenylsilyl)bicyclo[6.3.0]undecane

• 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: 1-acetyl-10-(tert-butyldiphenylsilyl)bicyclo[6.3.0]undecane
• 英文别名: 1-[(2R,3aS,9aS)-2-[tert-butyl(diphenyl)silyl]-1,2,3,4,5,6,7,8,9,9a-decahydrocyclopenta[8]annulen-3a-yl]ethanone
• 化学式: C₂₉H₄₀OSi
• 分子量: 432.721
• InChiKey: BFGYOAJEYDVZCE-WIDNXDAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.76
• 重原子数：
  31
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-acetyl-10-(tert-butyldiphenylsilyl)bicyclo[6.3.0]undecane 在 boron trifluoride diacetate 作用下， 以 二氯甲烷 为溶剂， 反应 336.0h， 以60%的产率得到1-acetylbicyclo[6.3.0]undecan-10-ol
  参考文献：
  名称：

  烯丙基硅烷的环加成 - 第 22 部分。¹ 通过路易斯酸促进的烯丙基硅烷的 [3+2] 和 [2+2] 环加成立体选择性合成环戊烷和环丁烷

  摘要：

  描述了路易斯酸的发展促进了 [3+2] 和 [2+2] 环加成，作为一种用于环戊烷和环丁烷立体选择性构建的新方法。介绍了这种方法在生物活性萜类天然产物的全合成中的优雅应用。1 引言 2 烯丙基硅烷的 [3+2] 环加成反应 2.1 甲硅烷基双环 [n.3.0] 烷烃的合成 2.2 甲硅烷基环戊烷的合成 2.3 炔酮的多米诺 [3+2] 环加成反应 2.4 甲硅烷基双环 [n.3.0] 烷烃的 [3+2] 环加成反应[3+2] 手性烯丙基硅烷的环加成反应 3 甲硅烷基环戊烷的转化 3.1 甲硅烷基双环 [n.3.0] 烷烃转化为对称烯烃 3.

  DOI：

  10.1055/s-0030-1258549
• 作为产物：
  描述：

  1-乙炔基-1-环辛醇 在 甲酸 、 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 1-acetyl-10-(tert-butyldiphenylsilyl)bicyclo[6.3.0]undecane
  参考文献：
  名称：

  Highly Stereoselective Synthesis of Bicyclo[n.3.0]alkanes by Titanium Tetrachloride Promoted [3 + 2] Cycloaddition of Allylsilanes and 1-Acetylcycloalkenes

  摘要：

  AbstractThe titanium tetrachloride promoted reaction of allylsilanes 1 with 1‐acetylcyclohexene is shown to afford the silylbicyclo[4.3.0]nonanes 9 ([3 + 2] cycloaddition products) along with the 1‐acetyl‐2‐allylcyclohexane 4 (Hosomi‐Sakurai product). Here we report that systematic variation of the substituents at the silicon atom of 1 allows suppression of the classical Hosomi‐Sakurai reaction in favor of the [3 + 2] cycloaddition. Cycloaddition of the allylsilanes 1 d, 1 i, and 1 k with 1‐acetylcycloalkenes 10, containing a 5‐, 6‐, 7‐, 8‐, or 12‐membered ring, gives rise to the corresponding silylbicyclo[n.3.0]alkanes 11 – 13. The cycloaddition of allyltriisopropylsilane (1 k) and 1‐acetyl‐2‐methylcycloalkenes 15 provides silylbicyclo[n.3.0]alkanes 16 with two contiguous quaternary carbon centers. The stereochemistry of the silylbicyclo[n.3.0]alkanes 11 a ‐ c and 14 is unambiguously determined by X‐ray analysis and 13C NMR spectroscopy.

  DOI：

  10.1002/chem.19970030409

文献信息

• Cycloadditions of Allylsilanes, Part 11. Stereoselective Synthesis of Hydroxycyclopentanes and Hydroxymethylcyclobutanes by Titanium Tetrachloride-Promoted [3+2] and [2+2] Cycloadditions of Sterically Hindered Allylsilanes and Subsequent Oxidative Cleavage of the Carbon-Silicon Bond
  作者：Hans-Joachim Knölker、Peter G. Jones、Günter Wanzl

  DOI：10.1055/s-1998-1727

  日期：1998.6

  Even highly sterically hindered organosilicon compounds containing the bulky tert-butyldiphenylsilyl group can be oxidatively cleaved to the corresponding carbinols using a modified protocol of the original Fleming-Tamao oxidation that generates the intermediate tert-butyldifluorosilyl derivatives. This novel application emphasizes the utility of allyl-tert-butyldiphenylsilane as a building block for the stereoselective synthesis of either hydroxycyclopentanes or hydroxymethylcyclobutanes via the sequence titanium tetrachloride-promoted cycloaddition and oxidative cleavage.

  即使高度立体阻碍的有机硅化合物含有笨重的叔丁基二苯基硅基，也可以使用改良的原始弗莱明-塔茂氧化方案氧化裂解为相应的羟基化合物，生成中间产物叔丁基二氟硅基衍生物。这种新颖的应用强调了烯丙基叔丁基二苯基硅烷作为立体选择性合成羟基环戊烷或羟甲基环丁烷的构建模块的实用性，其通过四氯化钛促进的环加成和氧化裂解反应进行。
• Highly Stereoselective Synthesis of Bicyclo[n.3.0]alkanes by Titanium Tetrachloride Promoted [3 + 2] Cycloaddition of Allylsilanes and 1-Acetylcycloalkenes
  作者：Hans-Joachim Knölker、Norbert Foitzik、Helmut Goesmann、Regina Graf、Peter G. Jones、Günter Wanzl

  DOI：10.1002/chem.19970030409

  日期：1997.4

  AbstractThe titanium tetrachloride promoted reaction of allylsilanes 1 with 1‐acetylcyclohexene is shown to afford the silylbicyclo[4.3.0]nonanes 9 ([3 + 2] cycloaddition products) along with the 1‐acetyl‐2‐allylcyclohexane 4 (Hosomi‐Sakurai product). Here we report that systematic variation of the substituents at the silicon atom of 1 allows suppression of the classical Hosomi‐Sakurai reaction in favor of the [3 + 2] cycloaddition. Cycloaddition of the allylsilanes 1 d, 1 i, and 1 k with 1‐acetylcycloalkenes 10, containing a 5‐, 6‐, 7‐, 8‐, or 12‐membered ring, gives rise to the corresponding silylbicyclo[n.3.0]alkanes 11 – 13. The cycloaddition of allyltriisopropylsilane (1 k) and 1‐acetyl‐2‐methylcycloalkenes 15 provides silylbicyclo[n.3.0]alkanes 16 with two contiguous quaternary carbon centers. The stereochemistry of the silylbicyclo[n.3.0]alkanes 11 a ‐ c and 14 is unambiguously determined by X‐ray analysis and 13C NMR spectroscopy.
• Cycloadditions of Allylsilanes - Part 22.¹ Stereoselective Synthesis of Cyclopentanes and Cyclobutanes by Lewis Acid Promoted [3+2] and [2+2] Cycloadditions of Allylsilanes
  作者：Hans-Joachim Knölker、Arndt Schmidt

  DOI：10.1055/s-0030-1258549

  日期：2010.9

  Lewis acid promoted [3+2] and [2+2] cycloadditions as a novel methodology for the stereoselective construction of cyclopentanes and cyclobutanes is described. Elegant applications of this methodology to the total synthesis of biologically active terpenoid natural products are presented. 1 Introduction 2 [3+2] Cycloadditions of Allylsilanes 2.1 Synthesis of Silylbicyclo[n.3.0]alkanes 2.2 Synthesis of Silylcyclopentanes

  描述了路易斯酸的发展促进了 [3+2] 和 [2+2] 环加成，作为一种用于环戊烷和环丁烷立体选择性构建的新方法。介绍了这种方法在生物活性萜类天然产物的全合成中的优雅应用。1 引言 2 烯丙基硅烷的 [3+2] 环加成反应 2.1 甲硅烷基双环 [n.3.0] 烷烃的合成 2.2 甲硅烷基环戊烷的合成 2.3 炔酮的多米诺 [3+2] 环加成反应 2.4 甲硅烷基双环 [n.3.0] 烷烃的 [3+2] 环加成反应[3+2] 手性烯丙基硅烷的环加成反应 3 甲硅烷基环戊烷的转化 3.1 甲硅烷基双环 [n.3.0] 烷烃转化为对称烯烃 3.