1-acetyl-8-(triphenylsilyl)bicyclo[4.3.0]nonane

• 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-8-(triphenylsilyl)bicyclo[4.3.0]nonane
• 英文别名: 1-[(2R,3aS,7aS)-2-triphenylsilyl-1,2,3,4,5,6,7,7a-octahydroinden-3a-yl]ethanone
• 化学式: C₂₉H₃₂OSi
• 分子量: 424.658
• InChiKey: GPPUKSIPWYTRLJ-TUMTZTIRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.09
• 重原子数：
  31
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 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-8-(triphenylsilyl)bicyclo[4.3.0]nonane 在 tetrafluoroboric acid 、 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 123.0h， 生成 (2,3,4,5,6,7-Hexahydro-1H-inden-2-yl)-triphenyl-silane
  参考文献：
  名称：

  Cycloadditions of Allylsilanes, Part 12. Regio- and Stereoselective Transformations of Silylbicyclo[n.3.0]alkanes

  摘要：

  在路易斯酸的促进下，1-乙酰基环烯烃和烯丙基硅烷发生[3 + 2]环加成反应，生成硅基双环[n.3.0]烷烃 4 和 5。通过区域选择性拜耳-维里格氧化和消除乙酸的顺序，可以得到 3-硅基双环[3.3.0]辛-1(5)-烯 8a 和 9a，以及 8-（三苯基硅基）双环[4.3.0]壬-1(6)-烯 (8b)。这些烯烃的环氧化和催化氢化反应具有完全的立体选择性，与硅烷取代基相反。对 8b 进行臭氧分解可得到 3-(三苯基硅基)环壬烷-1,5-二酮 (15)。

  DOI：

  10.1055/s-1999-3684
• 作为产物：
  描述：

  三苯基氯硅烷 、 alkaline earth salt of/the/ methylsulfuric acid 在 四氯化钛 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 1-acetyl-8-(triphenylsilyl)bicyclo[4.3.0]nonane
  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 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.
• Knoelker, Hans-Joachim; Foitzik, Norbert; Goesmann, Helmut, Angewandte Chemie, 1993, vol. 105, # 7, p. 1104 - 1106
  作者：Knoelker, Hans-Joachim、Foitzik, Norbert、Goesmann, Helmut、Graf, Regina

  DOI：——

  日期：——
• 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 12. Regio- and Stereoselective Transformations of Silylbicyclo[n.3.0]alkanes
  作者：Hans-Joachim Knölker、Norbert Foitzik、Christoph Gabler、Regina Graf

  DOI：10.1055/s-1999-3684

  日期：——

  Lewis acid promoted [3 + 2] cycloaddition of 1-acetylcycloalkenes and allylsilanes provides the silylbicyclo[n.3.0]-alkanes 4 and 5. The sequence of regioselective Bayer-Villiger oxidation and elimination of acetic acid affords the 3-silylbicyclo[3.3.0]oct-1(5)-enes 8a and 9a and the 8-(triphenylsilyl)bicyclo[4.3.0]non-1(6)-ene (8b). Epoxidation and catalytic hydrogenation of these olefins proceeds with complete stereoselectivity anti relative to the silyl substituent. Ozonolysis of 8b leads to 3-(triphenylsilyl)cyclononane-1,5-dione (15).

  在路易斯酸的促进下，1-乙酰基环烯烃和烯丙基硅烷发生[3 + 2]环加成反应，生成硅基双环[n.3.0]烷烃 4 和 5。通过区域选择性拜耳-维里格氧化和消除乙酸的顺序，可以得到 3-硅基双环[3.3.0]辛-1(5)-烯 8a 和 9a，以及 8-（三苯基硅基）双环[4.3.0]壬-1(6)-烯 (8b)。这些烯烃的环氧化和催化氢化反应具有完全的立体选择性，与硅烷取代基相反。对 8b 进行臭氧分解可得到 3-(三苯基硅基)环壬烷-1,5-二酮 (15)。