(2α,4aβ,8α,8aα)-Decahydro-2,8a-dimethyl-2,8-naphthalenediol 8-(methanesulfonate)

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (2α,4aβ,8α,8aα)-Decahydro-2,8a-dimethyl-2,8-naphthalenediol 8-(methanesulfonate)
• 英文别名: [(1R,4aR,7S,8aR)-7-hydroxy-7,8a-dimethyl-1,2,3,4,4a,5,6,8-octahydronaphthalen-1-yl] methanesulfonate
• 化学式: C₁₃H₂₄O₄S
• 分子量: 276.397
• InChiKey: UDCDINHRNVANNN-FVCCEPFGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  72
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2α,4aβ,8α,8aα)-Decahydro-2,8a-dimethyl-2,8-naphthalenediol 8-(methanesulfonate) 在 sodium tert-pentoxide 作用下， 以 甲苯 、 苯 为溶剂， 反应 0.17h， 以33%的产率得到4-<(1'α,2'α)-2'-(1-Methylethenyl)cyclopent-1'-yl>butan-2-one
  参考文献：
  名称：

  Rearrangement vs Homofragmentation: Chemical Consequences of Different .sigma.-Relays on the Heterolysis of Sulfonate Esters Induced by Through-Bond Interactions

  摘要：

  An alcoholate function intramolecularly induces heterolysis of a sulfonate ester group in an apolar solvent via orbital interactions through three intervening C-C single bonds (TBI). It is shown that the reactivity of rigid trans-perhydronaphthalene-1,4-diol monosulfonate esters (1-6) upon treatment with sodium tert-amylate in refluxing benzene is only affected by the relative position of the hydroxyl function to the sulfonate ester group and not by the orientation of the hydroxyl group. The two chief pathways by which these compounds react are rearrangement (1, 3, and 4) and homofragmentation (5 and 6). Stereoelectronic effects play a dominant role here, except in compound 2 where steric factors primarily determine the reactivity and product outcome (ether formation). Homofragmentation is much faster than rearrangement and is only possible when a 1,3-bridged through-space interaction accompanies TBI. The extent of TBI as well as the product composition is strongly determined by the sigma-relay of the three C-C bonds between the electron donor (alcoholate) and the electron acceptor (sulfonate ester bond). The results presented here are consistent with the trans rule and show the validity of similar proposals for biosynthetic processes.

  DOI：

  10.1021/jo00081a016
• 作为产物：
  描述：

  (+/-)-(4aS,8S,8aS)-8-hydroxy-8a-methyloctahydronaphthalen-2(1H)-one 在 吡啶 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 (2α,4aβ,8α,8aα)-Decahydro-2,8a-dimethyl-2,8-naphthalenediol 8-(methanesulfonate)
  参考文献：
  名称：

  Rearrangement vs Homofragmentation: Chemical Consequences of Different .sigma.-Relays on the Heterolysis of Sulfonate Esters Induced by Through-Bond Interactions

  摘要：

  An alcoholate function intramolecularly induces heterolysis of a sulfonate ester group in an apolar solvent via orbital interactions through three intervening C-C single bonds (TBI). It is shown that the reactivity of rigid trans-perhydronaphthalene-1,4-diol monosulfonate esters (1-6) upon treatment with sodium tert-amylate in refluxing benzene is only affected by the relative position of the hydroxyl function to the sulfonate ester group and not by the orientation of the hydroxyl group. The two chief pathways by which these compounds react are rearrangement (1, 3, and 4) and homofragmentation (5 and 6). Stereoelectronic effects play a dominant role here, except in compound 2 where steric factors primarily determine the reactivity and product outcome (ether formation). Homofragmentation is much faster than rearrangement and is only possible when a 1,3-bridged through-space interaction accompanies TBI. The extent of TBI as well as the product composition is strongly determined by the sigma-relay of the three C-C bonds between the electron donor (alcoholate) and the electron acceptor (sulfonate ester bond). The results presented here are consistent with the trans rule and show the validity of similar proposals for biosynthetic processes.

  DOI：

  10.1021/jo00081a016

文献信息

• Rearrangement vs Homofragmentation: Chemical Consequences of Different .sigma.-Relays on the Heterolysis of Sulfonate Esters Induced by Through-Bond Interactions
  作者：Romano V. A. Orru、Joannes B. P. A. Wijnberg、Catharina T. Bouwman、Aede de Groot

  DOI：10.1021/jo00081a016

  日期：1994.1

  An alcoholate function intramolecularly induces heterolysis of a sulfonate ester group in an apolar solvent via orbital interactions through three intervening C-C single bonds (TBI). It is shown that the reactivity of rigid trans-perhydronaphthalene-1,4-diol monosulfonate esters (1-6) upon treatment with sodium tert-amylate in refluxing benzene is only affected by the relative position of the hydroxyl function to the sulfonate ester group and not by the orientation of the hydroxyl group. The two chief pathways by which these compounds react are rearrangement (1, 3, and 4) and homofragmentation (5 and 6). Stereoelectronic effects play a dominant role here, except in compound 2 where steric factors primarily determine the reactivity and product outcome (ether formation). Homofragmentation is much faster than rearrangement and is only possible when a 1,3-bridged through-space interaction accompanies TBI. The extent of TBI as well as the product composition is strongly determined by the sigma-relay of the three C-C bonds between the electron donor (alcoholate) and the electron acceptor (sulfonate ester bond). The results presented here are consistent with the trans rule and show the validity of similar proposals for biosynthetic processes.