3-(2-Iodoethyl)cyclopentan-1-one | 134654-88-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2-Iodoethyl)cyclopentan-1-one
• 英文别名: 3-(2-iodoethyl)cyclopentanone
• CAS: 134654-88-9
• 化学式: C₇H₁₁IO
• 分子量: 238.068
• InChiKey: ZHCZZFWWUBYQJW-UHFFFAOYSA-N

物化性质

• 沸点：
  267.8±13.0 °C(Predicted)
• 密度：
  1.681±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(2-Iodoethyl)cyclopentan-1-one 在 tris(dibenzoylmethano)iron(III) samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以71%的产率得到1-norbornyl alcohol
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008
• 作为产物：
  描述：

  3-ethenyl-1-trimethylsiloxycyclopent-1-ene 在 盐酸 、 氢溴酸 、 sodium iodide 作用下， 以 正己烷 、 丙酮 为溶剂， 反应 12.0h， 生成 3-(2-Iodoethyl)cyclopentan-1-one
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008

文献信息

• Competing Radical- and Anion-Mediated Pathways in the Reduction of Bridgehead Tosylates with Lithium Aluminium Hydride
  作者：Ernest W. Della、Wit K. Janowski

  DOI：10.1071/ch98165

  日期：——

  Reaction of norborn-1-yl tosylate with lithium aluminium hydride in boiling tetrahydrofuran affords a mixture of norbornan-1-ol accompanied by the ring-opened products 4-methylcyclohexanol and 3-ethylcyclopentanol as their cis/trans isomers, as well as p-thiocresol and p-tolyl disulfide. Evidence strongly suggests that the reaction is mediated by the norborn-1-yloxy radical rather than the norborn-1-yloxy anion. The process is initiated by very slow acyl oxygen fission of the norbornyl tosylate, followed by reduction of the derived p-toluenesulfinate ion to give the p-thiocresoxide anion. Transfer of an electron from the latter to the substrate and decomposition of the derived norborn-1-yl tosylate radical anion leads to the norborn-1-yloxy radical which, upon ring opening, generates the monocyclic alcohols via the corresponding ketones. It is noteworthy that, when norborn-1-yl mesylate is exposed to lithium aluminium hydride, it yields norbornan-1-ol exclusively. In the absence of an efficient electron-transfer agent, the mechanism of reaction of norborn-1-yl mesylate is suggested to involve acyl oxygen fission only.

  在沸腾的四氢呋喃中，降冰片烷-1-基甲苯磺酸盐与氢化铝锂发生反应 在沸腾的四氢呋喃中与氢化铝锂反应，生成降冰片烷-1-醇的混合物，同时生成 4-甲基环己醇和 3-乙基环戊醇的开环产物。 开环产物 4-甲基环己醇和 3-乙基环戊醇的混合物。 顺/反异构体，以及 对硫代甲酚和对甲苯基 二硫化物。证据有力地表明，该反应是由 而不是降冰片-1-氧基阴离子。该过程 是由非常缓慢的酰氧基裂解降冰片酰基对甲苯磺酸盐开始的，然后由衍生的对甲苯磺酸盐还原 生成的对甲苯磺酸离子被还原，生成对硫代甲磺酸阴离子。 生成对硫代甲磺酸阴离子。电子 电子转移到底物上，并分解衍生出的降冰片-1-基 基阴离子分解，产生降冰片-1-基氧基基，该基在开环后生成单环化合物。 开环后，通过相应的酮生成单环醇。值得注意的是 值得注意的是，当降冰片-1-基甲磺酸酯与铝氢化锂接触时 氢化锂时，只生成降冰片烷-1-醇。如果没有有效的 在缺乏有效电子转移剂的情况下，降冰片-1-基甲磺酸酯的反应机理被认为涉及酰基氧裂变。 建议只涉及酰基氧裂变。
• MOLANDER, GARY A.;MCKIE, JEFFREY A., J. ORG. CHEM., 56,(1991) N3, C. 4112-4120
  作者：MOLANDER, GARY A.、MCKIE, JEFFREY A.

  DOI：——

  日期：——