8-((2S,3R)-3-Iodomethyl-oxiranylmethyl)-7-methyl-1,4-dioxa-spiro[4.5]dec-7-ene | 1026738-21-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 8-((2S,3R)-3-Iodomethyl-oxiranylmethyl)-7-methyl-1,4-dioxa-spiro[4.5]dec-7-ene
• 英文别名: 8-[[(2S,3R)-3-(iodomethyl)oxiran-2-yl]methyl]-7-methyl-1,4-dioxaspiro[4.5]dec-7-ene
• CAS: 1026738-21-5
• 化学式: C₁₃H₁₉IO₃
• 分子量: 350.197
• InChiKey: LKIRSQVFVDKCIZ-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  31
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  8-((2S,3R)-3-Iodomethyl-oxiranylmethyl)-7-methyl-1,4-dioxa-spiro[4.5]dec-7-ene 在 溶剂黄146 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (S)-1-(7-Methyl-1,4-dioxa-spiro[4.5]dec-7-en-8-yl)-but-3-en-2-ol 、 (R)-1-(7-Methyl-1,4-dioxa-spiro[4.5]dec-7-en-8-yl)-but-3-en-2-ol
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.

  DOI：

  10.1021/jo00085a037
• 作为产物：
  描述：

  7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-甲醛 在 吡啶 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 正丁基锂 、 三氯化铝 、 草酰氯 、 L-(+)-酒石酸二乙酯 、 dimethyl sulfide borane 、 4 A molecular sieve 、 双氧水 、 sodium hydride 、 二甲基亚砜 、 三乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 异辛烷 、 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 18.0h， 生成 8-((2S,3R)-3-Iodomethyl-oxiranylmethyl)-7-methyl-1,4-dioxa-spiro[4.5]dec-7-ene
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.

  DOI：

  10.1021/jo00085a037