rel-(1R,2R,5S,7R)-2-carbomethoxy-7-chloro-3-oxabicyclo-<3.3.1>-7-nonane | 121223-29-8

• 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: rel-(1R,2R,5S,7R)-2-carbomethoxy-7-chloro-3-oxabicyclo-<3.3.1>-7-nonane
• 英文别名: methyl (1S,2S,5R,7S)-7-chloro-3-oxabicyclo[3.3.1]nonane-2-carboxylate
• CAS: 121223-29-8
• 化学式: C₁₀H₁₅ClO₃
• 分子量: 218.68
• InChiKey: QHHVHXLVEVJMOU-XGEHTFHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3-环己烯-1-甲醇 在 4-二甲氨基吡啶 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 2.25h， 生成 rel-(1R,2R,5S,7R)-2-carbomethoxy-7-chloro-3-oxabicyclo-<3.3.1>-7-nonane
  参考文献：
  名称：

  Synthesis of oxacyclic carboxylic esters by way of methoxycarbonyloxonium ions; Evidence for a cationic oxa-cope rearrangement

  摘要：

  DOI：

  10.1016/s0040-4039(00)82348-5

文献信息

• π-Cyclizations of α-methoxycarbonyl oxycarbenium ions; synthesis of oxacyclic carboxylic esters
  作者：Lucie D.M. Lolkema、Henk Hiemstra、Cindy Semeyn、W.Nico Speckamp

  DOI：10.1016/s0040-4020(01)85238-8

  日期：1994.1

  Acid-mediated cyclization reactions are described of seven methyl 2-acetoxy-2-(3-alken-1-oxy)acetates with different chain substitution. The major product of the tin tetrachloride-induced cyclization reaction is in most cases a tetrahydropyran containing an equatorial carbomethoxy function at C2 and an axial chlorine atom at C4. The mechanism of its formation involves a net cis-addition of the intermediate alpha-ester oxycarbenium ion to the carbon-carbon double bond, most likely caused by a quasi axial orientation of the ester function in a chair-like transition state. The results are interpreted by invoking (1) the occurrence of a 2-oxonia-Cope rearrangement and (2) the participation of the ester function in the mechanism of cyclization by trapping the cyclic cationic intermediate. The cyclizations of two methyl 2-acetoxy-2-(4-alken-1-oxy)acetates and two methyl 2-acetoxy-2-(alkynoxy)acetates are also described .