1-hydroxybicyclo<2.2.2>octan-2-one tert-butyldimethylsilyl ether | 135107-28-7

• 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-hydroxybicyclo<2.2.2>octan-2-one tert-butyldimethylsilyl ether
• 英文别名: 1-hydroxybicyclo<2.2.2>octan-2-one t-butyldimethylsilyl ether；1-{[tert-Butyl(dimethyl)silyl]oxy}bicyclo[2.2.2]octan-2-one；1-[tert-butyl(dimethyl)silyl]oxybicyclo[2.2.2]octan-2-one
• CAS: 135107-28-7
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: DYRKKWBONMCAIS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  1-hydroxybicyclo<2.2.2>octan-2-one tert-butyldimethylsilyl ether 在 2,6-二甲基吡啶 作用下， 生成 1-Ethoxy-(E)-2-ethylidenebicyclo<2.2.2>octane
  参考文献：
  名称：

  Takeuchi, K.; Ohga, Y.; Kitagawa, T., Journal de Chimie Physique et de Physico-Chimie Biologique, 1992, vol. 89, # 7, p. 1631 - 1638

  摘要：

  DOI：
• 作为产物：
  描述：

  二环[2.2.2]辛烷-1,2-二醇 生成 1-hydroxybicyclo<2.2.2>octan-2-one tert-butyldimethylsilyl ether
  参考文献：
  名称：

  Takeuchi, K.; Ohga, Y.; Kitagawa, T., Journal de Chimie Physique et de Physico-Chimie Biologique, 1992, vol. 89, # 7, p. 1631 - 1638

  摘要：

  DOI：

文献信息

• Solvolysis of 2-methylene bicyclic bridgehead derivatives: a model for gradual variation of .pi.-conjugation in carbocations
  作者：Kenichi Takeuchi、Toshikazu Kitagawa、Yasushi Ohga、Masayasu Yoshida、Fumio Akiyama、Akio Tsugeno

  DOI：10.1021/jo00027a050

  日期：1992.1

  The rates of solvolysis in ethanol or 80% ethanol at 25-degrees-C have been determined on 2-methylenebicyclo[2.2.2]oct-1-yl triflate (4a), 2-methylenebicyclo[3.2.1]oct-1-yl triflate (5a), 2-methylenebicyclo[3.2.2]non-1-yl mesylate (6a), 2-methylenebicyclo[3.3.1]non-1-yl mesylate (7a-OMs) and heptafluorobutyrate (7a-OHFB), 1-chloro-2-methylenebicyclo[4.2.2]decane (8a), 2-methylenebicyclo[4.3.1]dec-1-yl trifluoroacetate (9a), and 4-methylene-3-homoadamantyl heptafluorobutyrate (10a) and on their corresponding parent 1-bicycloalkyl and 3-homoadamantyl derivatives 4b-10b containing the respective leaving group. The rate ratios for 4a/4b, 5a/5b, 10a/10b, 6a/6b, 7a/7b, 8a/8b, and 9a/9b are 10(-3.9), 10(-1.9), 10(-1.1), 10(0.8), 10(0.9) (for mesylate), 10(-0.2), and 10(0.7), respectively. A plot of the logarithms of the rate ratios against olefinic strain energies of their corresponding unsubstituted bridgehead olefins shows that the smaller the olefinic strain energy, the greater the rate ratio, providing a methodology to gradually change the conjugative ability of bridgehead carbocations. The enhancement of allylic conjugation with increasing skeletal flexibility has been further verified by the enhanced solvolysis rate of (E)-2-ethylidenebicyclo[3.2.2]non-1-yl mesylate ((E)-6e) relative to 6a by a factor of 259. A similar study on much more rigid (E)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflate ((E)-4e) gave a (E)-4e/4a rate ratio of 6.3. AM1 semiempirical molecular orbital calculations on pertinent 2-methylene and (E)-2-ethylidene bridgehead carbocations and corresponding hydrocarbons (L = hydrogen) also supported the increase in the conjugation with increasing skeletal flexibility. The solvolysis products were solely bridgehead substitution products, no indication for the formation of bridgehead olefin via an S(N)1' mechanism having been obtained.
• Marked leaving group strain in (Z)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflate and its significant relief in (Z)-2-ethylidenebicyclo[3.2.2]non-1-yl mesylate
  作者：Kenichi Takeuchi、Yasushi Ohga、Toshikazu Kitagawa

  DOI：10.1021/jo00017a003

  日期：1991.8

  The rate of ethanolysis at 25-degrees-C of (Z)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflate [(Z)-3] is 217 times faster than that of its E isomer, whereas more flexible (Z)-2-ethylidenebicyclo[3.2.2]non-1-yl mesylate solvolyzes 3.4 times slower than its E isomer, indicating marked leaving-group strain in the ground state of (Z)-3, which is supported by MM2 calculations.
• Takeuchi, K.; Ohga, Y.; Kitagawa, T., Journal de Chimie Physique et de Physico-Chimie Biologique, 1992, vol. 89, # 7, p. 1631 - 1638
  作者：Takeuchi, K.、Ohga, Y.、Kitagawa, T.

  DOI：——

  日期：——