1-bromo-3-iodobicyclo[1.1.1]pentane

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 英文名称: 1-bromo-3-iodobicyclo[1.1.1]pentane
• 化学式: C₅H₆BrI
• 分子量: 272.911
• InChiKey: KTDWIFYIROXOLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-bromo-3-iodobicyclo[1.1.1]pentane 、 α-环糊精 以 水 为溶剂， 反应 3.0h， 以81%的产率得到
  参考文献：
  名称：

  双环[1.1.1]戊烷衍生物的α-环糊精包封：制备[1.1.1]丙烷的可储存原料

  摘要：

  双环[1.1.1]戊烷（BCP）支架可用于药物化学，许多协议可用于由[1.1.1]丙炔合成BCP衍生物。在这里，我们报告（1）BCP衍生物的α-环糊精（α-CD）包封，提供了一种稳定，易于储存的材料，可以从中轻松，定量地回收BCP，以及（2）1种脱碘反应的新方法和简单方法，3-二碘代BCP在质子/非质子/极性/非极性溶剂中提供[1.1.1]丙炔。这些方法的组合可在温和条件下，从含有1,3-二碘代BCP的α-CD胶囊中，按需简单，按需制备[1.1.1]丙炔。

  DOI：

  10.1002/anie.202014997
• 作为产物：
  描述：

  1,3-二碘双环[1.1.1]戊烷 在 溴 作用下， 以 四氯化碳 为溶剂， 以14%的产率得到1-bromo-3-iodobicyclo[1.1.1]pentane
  参考文献：
  名称：

  Formation and Reactions of Bicyclo[1.1.1]pentyl-1 Cations

  摘要：

  The ionization of l-bicyclo[1.1.1]pentyl halides was shown to initially form the 1,3-bridged bicycle[1.1.1]pentyl-l cation. It appears to be a transition state that leads to the bicyclo[1.1.0]butyl-1-carbinyl cation which can be trapped with azide ion and can be directly observed by NMR in SO2CIF. Although the major products of solvolysis of the halides are 3-methylenecyclobutyl derivatives, the corresponding cation was calculated to have a significantly higher energy than the bicyclobutylcarbinyl ion. Therefore, the products are probably formed by an attack of the nucleophile on the latter ion, accompanied by bond migration. The bridgehead iodide reacts under solvolytic conditions with azide ion to form bicyclo[1.1.0]butyl-l azide as a product. It also reacts with potassium hydroxide to give [1.1.1]propellane, and the same reaction occurs on dissolving in acetonitrile or pyridine. The reaction of 1,3-diiodobicyclo[1.1.1]pentane with ethoxide ion also was found to give [1.1.1]propellane via a nucleophilic attack on one of the iodines. The propellane reacts with methyl hypoiodite to give 3-iodobicyclo[1.1.1]pentyl-l cation, which can react with methanol to give 3-methoxybicyclo[1.1.1]pentyl-l iodide and with azide ion to give 3-iodobicyclo[1.1.1]pentyl-1 azide. These data provide evidence for a discrete 3-iodobicyclo[1.1.1]pentyl-l cation intermediate. The effect of substituents on the rate of solvolysis of bicyclo[1.1.1]pentyl-l iodide was studied. With 3-aryl substituents, a value of rho = -1.7 was found, which is similar to that observed in the solvolysis of 3-arylcyclobutyl tosylates (rho = -1.6). The 3-substituted bicyclopentyl halides usually form the corresponding 3-methylenecyclobutyl cations rather than bicyclo[1.1.0]butyl-1-carbinyl ions, because most substituents will help stabilize the former type of ion.

  DOI：

  10.1021/ja00105a046

文献信息

• Trapping the 3-Halobicyclo[1.1.1]pent-1-yl Cation. Mechanistic Implications and Synthesis of Mixed 1,3-Dihalobicyclo[1.1.1]pentanes
  作者：Ian R. Milne、Dennis K. Taylor

  DOI：10.1021/jo9722764

  日期：1998.5.1
• Synthesis of Some Bridgehead-Bridgehead-Disubstituted Bicyclo[1.1.1]pentanes
  作者：Ernest W. Della、Dennis K. Taylor

  DOI：10.1021/jo00090a015

  日期：1994.6

  The synthesis of a wide variety of 1,3-disubstituted bicyclo[1.1.1]pentanes is described, with particular emphasis on the generation of a series of S-X-substituted bicyclo[1.1.1]pentyl bromides required for solvolytic studies. Functional group manipulation at the bridgehead was readily accomplished in the majority of cases by radical processes in some instances, transformations were effected via carbanionic-type intermediates.
• Formation and Reactions of Bicyclo[1.1.1]pentyl-1 Cations
  作者：Kenneth B. Wiberg、Neil McMurdie

  DOI：10.1021/ja00105a046

  日期：1994.12

  The ionization of l-bicyclo[1.1.1]pentyl halides was shown to initially form the 1,3-bridged bicycle[1.1.1]pentyl-l cation. It appears to be a transition state that leads to the bicyclo[1.1.0]butyl-1-carbinyl cation which can be trapped with azide ion and can be directly observed by NMR in SO2CIF. Although the major products of solvolysis of the halides are 3-methylenecyclobutyl derivatives, the corresponding cation was calculated to have a significantly higher energy than the bicyclobutylcarbinyl ion. Therefore, the products are probably formed by an attack of the nucleophile on the latter ion, accompanied by bond migration. The bridgehead iodide reacts under solvolytic conditions with azide ion to form bicyclo[1.1.0]butyl-l azide as a product. It also reacts with potassium hydroxide to give [1.1.1]propellane, and the same reaction occurs on dissolving in acetonitrile or pyridine. The reaction of 1,3-diiodobicyclo[1.1.1]pentane with ethoxide ion also was found to give [1.1.1]propellane via a nucleophilic attack on one of the iodines. The propellane reacts with methyl hypoiodite to give 3-iodobicyclo[1.1.1]pentyl-l cation, which can react with methanol to give 3-methoxybicyclo[1.1.1]pentyl-l iodide and with azide ion to give 3-iodobicyclo[1.1.1]pentyl-1 azide. These data provide evidence for a discrete 3-iodobicyclo[1.1.1]pentyl-l cation intermediate. The effect of substituents on the rate of solvolysis of bicyclo[1.1.1]pentyl-l iodide was studied. With 3-aryl substituents, a value of rho = -1.7 was found, which is similar to that observed in the solvolysis of 3-arylcyclobutyl tosylates (rho = -1.6). The 3-substituted bicyclopentyl halides usually form the corresponding 3-methylenecyclobutyl cations rather than bicyclo[1.1.0]butyl-1-carbinyl ions, because most substituents will help stabilize the former type of ion.
• α‐Cyclodextrin Encapsulation of Bicyclo[1.1.1]pentane Derivatives: A Storable Feedstock for Preparation of [1.1.1]Propellane
  作者：Tadafumi Matsunaga、Junichiro Kanazawa、Tomohiro Ichikawa、Mei Harada、Yusuke Nishiyama、Nghia Tuan Duong、Takashi Matsumoto、Kazunori Miyamoto、Masanobu Uchiyama

  DOI：10.1002/anie.202014997

  日期：2021.2

  The bicyclo[1.1.1]pentane (BCP) scaffold is useful in medicinal chemistry, and many protocols are available for synthesizing BCP derivatives from [1.1.1]propellane. Here, we report (1) the α‐cyclodextrin (α‐CD) encapsulation of BCP derivatives, affording a stable, readily storable material from which BCPs can be easily and quantitatively recovered and (2) new and simple protocols for deiodination reaction

  双环[1.1.1]戊烷（BCP）支架可用于药物化学，许多协议可用于由[1.1.1]丙炔合成BCP衍生物。在这里，我们报告（1）BCP衍生物的α-环糊精（α-CD）包封，提供了一种稳定，易于储存的材料，可以从中轻松，定量地回收BCP，以及（2）1种脱碘反应的新方法和简单方法，3-二碘代BCP在质子/非质子/极性/非极性溶剂中提供[1.1.1]丙炔。这些方法的组合可在温和条件下，从含有1,3-二碘代BCP的α-CD胶囊中，按需简单，按需制备[1.1.1]丙炔。