(-)-(1R,2S,5S,6R,8R)-5,6-epoxy-8-isopropenyl-1-methyl-2-(trimethylsilyl)bicyclo<4.4.0>decane | 137895-84-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (-)-(1R,2S,5S,6R,8R)-5,6-epoxy-8-isopropenyl-1-methyl-2-(trimethylsilyl)bicyclo<4.4.0>decane
• 英文别名: [(1aS,4S,4aR,7R,8aR)-4a-methyl-7-prop-1-en-2-yl-1a,2,3,4,5,6,7,8-octahydronaphtho[4,4a-b]oxiren-4-yl]-trimethylsilane
• CAS: 137895-84-2
• 化学式: C₁₇H₃₀OSi
• 分子量: 278.51
• InChiKey: FCUHRZIMLKSTDZ-XAJHFOFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.01
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-(1R,2S,5S,6R,8R)-5,6-epoxy-8-isopropenyl-1-methyl-2-(trimethylsilyl)bicyclo<4.4.0>decane 在 3,5-二甲基吡唑 、 ferric(III) bromide 、 二氯氧化铬 、 叔丁醇 作用下， 以 二氯甲烷 为溶剂， 反应 182.5h， 生成 solavetivone
  参考文献：
  名称：

  Silicon-promoted ring contractions in the formation of carbocyclic spiro compounds. Total synthesis of (-)-solavetivone

  摘要：

  A new method involving silicon-promoted ring contraction was developed for the synthesis of carbocyclic spiro compounds. In the presence of a Lewis acid, (trimethylsilyl)decalinol 12 and (trimethylsilyl)declain expoide 11 underwent ring contraction in a highly stereoselective manner to afford spiro[4.5]dec-6-enes 14 and 19, respectively. The first total synthesis of optically active solavetivone ((-)-1) was accomplished in 13 steps by use of this new type of reaction as the key step. Utilization of the silicon-promoted ring contraction solves three problems associated with spiro compound synthesis: (1) efficient generation of the quaternary carbon spiro center, (2) full control of the stereoconfiguration of the spiro center during its formation, and (3) stereospecific establishment of chiral centers on both rings of the spiro unit.

  DOI：

  10.1021/jo00029a025
• 作为产物：
  描述：

  7(R)-Isopropenyl-4a(S)-methyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one 在 三氟化硼乙醚 、 氨 、 甲基锂 、 calcium 、 间氯过氧苯甲酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醚 、 氯仿 为溶剂， 反应 53.38h， 生成 (-)-(1R,2S,5S,6R,8R)-5,6-epoxy-8-isopropenyl-1-methyl-2-(trimethylsilyl)bicyclo<4.4.0>decane
  参考文献：
  名称：

  Silicon-promoted ring contractions in the formation of carbocyclic spiro compounds. Total synthesis of (-)-solavetivone

  摘要：

  A new method involving silicon-promoted ring contraction was developed for the synthesis of carbocyclic spiro compounds. In the presence of a Lewis acid, (trimethylsilyl)decalinol 12 and (trimethylsilyl)declain expoide 11 underwent ring contraction in a highly stereoselective manner to afford spiro[4.5]dec-6-enes 14 and 19, respectively. The first total synthesis of optically active solavetivone ((-)-1) was accomplished in 13 steps by use of this new type of reaction as the key step. Utilization of the silicon-promoted ring contraction solves three problems associated with spiro compound synthesis: (1) efficient generation of the quaternary carbon spiro center, (2) full control of the stereoconfiguration of the spiro center during its formation, and (3) stereospecific establishment of chiral centers on both rings of the spiro unit.

  DOI：

  10.1021/jo00029a025

文献信息

• Comparison of the electronic effect and the steric influence between the 1,1,2,2,2-pentamethyldisilanyl and the trimethylsilyl groups
  作者：Jih Ru Hwu、John M. Wetzel、John S. Lee、Raymond J. Butcher

  DOI：10.1016/0022-328x(93)80322-3

  日期：1993.6

  A comparison of the electronic effects expressed by the Me3SiMe2Si-; and Me3Si- groups towards carbocationic intermediates was made by study of acid-catalyzed rearrangements of decalin epoxides 3 and 4. Reaction of the Me3SiMe2Si-epoxide 3 with BF3 · Et2O in CH2Cl2 at -50°C gave four products: B-ring contracted spirocyclic alcohol 9 (21%), methyl-migrated decanol 12 (23%), A-ring contracted aldehyde

  Me 3 SiMe 2 Si-;表示的电子效应的比较；通过研究十氢化萘环氧化物3和4的酸催化重排，制得了朝向碳阳离子中间体的Me和Si 3和Si 3-。Me 3 SiMe 2 Si-环氧化合物3与BF 3 ·Et 2 O在CH 2 Cl 2中在-50°C下反应，得到四种产物：B环缩合的螺环醇9（21％），甲基迁移的癸醇12（ 23％），A环缩醛15（21％）和氟代醇17（14％）。在相同条件下中，Me 3 Si的环氧化物4，得到醇9（24％），癸醇12（18％），醛16（23％; CF。15），和fluorohydrin 18（13％; CF。17）。这些结果表明，Me 3 SiMe 2 Si-和Me 3 Si-基团对碳正离子具有相同程度的电子影响。