(3aα,3bβ,6aβ,6bα)-1,2,3,3a,6a,6b-hexahydro-3a,4-dimethyl-5-(trimethylsilyl)spiro[cyclobuta[1,2:3,4]dicyclopentene-1(3bH),2'-[1,3]-dioxolan]-6-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aα,3bβ,6aβ,6bα)-1,2,3,3a,6a,6b-hexahydro-3a,4-dimethyl-5-(trimethylsilyl)spiro[cyclobuta[1,2:3,4]dicyclopentene-1(3bH),2'-[1,3]-dioxolan]-6-one
• 英文别名: (1'S,2'R,6'S,7'R)-5',7'-dimethyl-4'-trimethylsilylspiro[1,3-dioxolane-2,10'-tricyclo[5.3.0.02,6]dec-4-ene]-3'-one
• 化学式: C₁₇H₂₆O₃Si
• 分子量: 306.477
• InChiKey: WOHUIIUVSVBSSX-GVAFMPQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aα,3bβ,6aβ,6bα)-1,2,3,3a,6a,6b-hexahydro-3a,4-dimethyl-5-(trimethylsilyl)spiro[cyclobuta[1,2:3,4]dicyclopentene-1(3bH),2'-[1,3]-dioxolan]-6-one 在 palladium on activated charcoal 盐酸 、 sodium tetrahydroborate 、 氢气 、 对甲苯磺酰肼 作用下， 以 乙酸乙酯 为溶剂， 反应 83.0h， 生成 (1R,2S,6R,7S,8S)-6,8-dimethyltricyclo[5.3.0.02,6]decan-3-one
  参考文献：
  名称：

  Synthesis of the Spatane Nucleus (cis-anti-cis-tricyclo[5.3.0.0^2,6]decane) using the Pauson−Khand Reaction with a Remarkable Reversal in Regioselectivity

  摘要：

  The Pauson-Khand reaction of cyclobutenes 3-5 with a variety of acetylenes yielded cis-anti cis-tricyclo[5.3.0.0(2,6)] decanes 9-17. The unwanted regioisomers 9a and 10a were the sole products using acetylene, but there was a remarkable reversal in orientation of the cyclobutene component yielding the desired regioisomer 13b upon using (trimethylsilyl)acetylene. The importance of the allylic methyl group in the cyclobutenes in directing the regiochemical outcome was substantiated by the lack of selectivity in Pauson-Khand reactions of desmethylcyclobutene 5 with acetylene and (trimethylsilyl)acetylene. The relative unimportance of electronic control of regiochemistry was concluded from the consistent ratio of Pauson-Khand reaction products from norbornenone 22 with various acetylenes. A hypothesis rationalizing the regiochemical outcome was based on steric interactions of the allylic methyl roup from the cyclobutene component with either the smaller acetylene substituent or the CO ligands on the cobalt. This steric interaction was further hypothesized to be influenced by the larger acetylene substituent sterically crowding the CO ligands on the cobalt.

  DOI：

  10.1021/jo9708194
• 作为产物：
  描述：

  6,7-dichloro-5-methylspiro(bicyclo[3.2.0]heptane-2,2'-[1,3]dioxolane) 在 sodium naphthalenide 作用下， 以 四氢呋喃 、 癸烷 为溶剂， 反应 75.33h， 生成 (3aα,3bβ,6aβ,6bα)-1,2,3,3a,6a,6b-hexahydro-3a,4-dimethyl-5-(trimethylsilyl)spiro[cyclobuta[1,2:3,4]dicyclopentene-1(3bH),2'-[1,3]-dioxolan]-6-one
  参考文献：
  名称：

  Synthesis of the Spatane Nucleus (cis-anti-cis-tricyclo[5.3.0.0^2,6]decane) using the Pauson−Khand Reaction with a Remarkable Reversal in Regioselectivity

  摘要：

  The Pauson-Khand reaction of cyclobutenes 3-5 with a variety of acetylenes yielded cis-anti cis-tricyclo[5.3.0.0(2,6)] decanes 9-17. The unwanted regioisomers 9a and 10a were the sole products using acetylene, but there was a remarkable reversal in orientation of the cyclobutene component yielding the desired regioisomer 13b upon using (trimethylsilyl)acetylene. The importance of the allylic methyl group in the cyclobutenes in directing the regiochemical outcome was substantiated by the lack of selectivity in Pauson-Khand reactions of desmethylcyclobutene 5 with acetylene and (trimethylsilyl)acetylene. The relative unimportance of electronic control of regiochemistry was concluded from the consistent ratio of Pauson-Khand reaction products from norbornenone 22 with various acetylenes. A hypothesis rationalizing the regiochemical outcome was based on steric interactions of the allylic methyl roup from the cyclobutene component with either the smaller acetylene substituent or the CO ligands on the cobalt. This steric interaction was further hypothesized to be influenced by the larger acetylene substituent sterically crowding the CO ligands on the cobalt.

  DOI：

  10.1021/jo9708194

文献信息

• Synthesis of the Spatane Nucleus (<i>cis</i>-<i>anti</i>-<i>cis</i>-tricyclo[5.3.0.0^2,6]decane) using the Pauson−Khand Reaction with a Remarkable Reversal in Regioselectivity
  作者：Bruce A. Kowalczyk、Timothy C. Smith、William G. Dauben

  DOI：10.1021/jo9708194

  日期：1998.3.1

  The Pauson-Khand reaction of cyclobutenes 3-5 with a variety of acetylenes yielded cis-anti cis-tricyclo[5.3.0.0(2,6)] decanes 9-17. The unwanted regioisomers 9a and 10a were the sole products using acetylene, but there was a remarkable reversal in orientation of the cyclobutene component yielding the desired regioisomer 13b upon using (trimethylsilyl)acetylene. The importance of the allylic methyl group in the cyclobutenes in directing the regiochemical outcome was substantiated by the lack of selectivity in Pauson-Khand reactions of desmethylcyclobutene 5 with acetylene and (trimethylsilyl)acetylene. The relative unimportance of electronic control of regiochemistry was concluded from the consistent ratio of Pauson-Khand reaction products from norbornenone 22 with various acetylenes. A hypothesis rationalizing the regiochemical outcome was based on steric interactions of the allylic methyl roup from the cyclobutene component with either the smaller acetylene substituent or the CO ligands on the cobalt. This steric interaction was further hypothesized to be influenced by the larger acetylene substituent sterically crowding the CO ligands on the cobalt.