(1S,4R,5S,6R)-5,6-Bis-methanesulfonyloxy-bicyclo[2.2.2]oct-2-ene-2,3-dicarboxylic acid dimethyl ester | 137927-47-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1S,4R,5S,6R)-5,6-Bis-methanesulfonyloxy-bicyclo[2.2.2]oct-2-ene-2,3-dicarboxylic acid dimethyl ester
• 英文别名: dimethyl (1R,4S,5R,6S)-5,6-bis(methylsulfonyloxy)bicyclo[2.2.2]oct-2-ene-2,3-dicarboxylate
• CAS: 137927-47-0
• 化学式: C₁₄H₂₀O₁₀S₂
• 分子量: 412.439
• InChiKey: DDHLDIYEYVJNEM-IVQVNHIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  156
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  重氮甲烷 、 (1S,4R,5S,6R)-5,6-Bis-methanesulfonyloxy-bicyclo[2.2.2]oct-2-ene-2,3-dicarboxylic acid dimethyl ester 生成 (1S,2S,6R,7R,8S,9R)-8,9-Bis-methanesulfonyloxy-3,4-diaza-tricyclo[5.2.2.0^2,6]undec-3-ene-2,6-dicarboxylic acid dimethyl ester 、 (1R,2S,6R,7S,8R,9S)-8,9-Bis-methanesulfonyloxy-3,4-diaza-tricyclo[5.2.2.0^2,6]undec-3-ene-2,6-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Diastereofacial selectivity in 1,3-dipolar cycloadditions. Reactions of diazomethane with endo,cis-5,6-disubstituted bicyclo[2.2.2]oct-2-enes.

  摘要：

  The reaction of diazomethane with endo,cis-5,6-diacetoxy, dimesyloxy, bis(methoxycarbonyl) and dihydroxybicyclo[2.2.2]oct-2-ene derivatives, respectively, afforded either only the anti adduct or a mixture of anti and syn adducts wherein the anti diasteroisomer was highly dominant (greater-than-or-equal-to 10:1). The observed facial selectivity provides convincing evidence that direct through space interactions between the attacking 1,3-dipole and acetoxy, hydroxy etc. substituents are, as a whole, repulsive. Steric ''non-bonded'' repulsions and dipole-dipole interactions override possible stabilizing interactions, e.g. orbital interactions and hydrogen bonding effects.

  DOI：

  10.1016/s0040-4020(01)88294-6
• 作为产物：
  描述：

  (1S,4R,5S,6R)-5,6-Dihydroxy-bicyclo[2.2.2]oct-2-ene-2,3-dicarboxylic acid dimethyl ester 、 甲基磺酰氯 在 三乙胺 作用下， 以51%的产率得到(1S,4R,5S,6R)-5,6-Bis-methanesulfonyloxy-bicyclo[2.2.2]oct-2-ene-2,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Diastereofacial selectivity in 1,3-dipolar cycloadditions. Reactions of diazomethane with endo,cis-5,6-disubstituted bicyclo[2.2.2]oct-2-enes.

  摘要：

  The reaction of diazomethane with endo,cis-5,6-diacetoxy, dimesyloxy, bis(methoxycarbonyl) and dihydroxybicyclo[2.2.2]oct-2-ene derivatives, respectively, afforded either only the anti adduct or a mixture of anti and syn adducts wherein the anti diasteroisomer was highly dominant (greater-than-or-equal-to 10:1). The observed facial selectivity provides convincing evidence that direct through space interactions between the attacking 1,3-dipole and acetoxy, hydroxy etc. substituents are, as a whole, repulsive. Steric ''non-bonded'' repulsions and dipole-dipole interactions override possible stabilizing interactions, e.g. orbital interactions and hydrogen bonding effects.

  DOI：

  10.1016/s0040-4020(01)88294-6