4-methylcubane-1-iodide | 125762-85-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4-methylcubane-1-iodide
• 英文别名: 4-iodo-1-methylcubane；4-Methylcubyl iodide；1-iodo-4-methylcubane
• CAS: 125762-85-8
• 化学式: C₉H₉I
• 分子量: 244.075
• InChiKey: ONDAYBPCNULAQB-UHFFFAOYSA-N

物化性质

• 沸点：
  227.7±9.0 °C(Predicted)
• 密度：
  2.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  6.0
• 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：

  4-methylcubane-1-iodide 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 反应 0.25h， 以74%的产率得到methyl cubane
  参考文献：
  名称：

  The preparation and fate of cubylcarbinyl radicals

  摘要：

  The cubylcarbinyl radical has been generated from cubylcarbinyl bromide and from the N-hydroxy-2-pyridinethione ester of cubylacetic acid under various conditions favoring hydrogen-atom transfer to the radical. Only when selenophenol in high concentration is used as the hydrogen donor is any methylcubane formed. Otherwise the cubylcarbinyl radical rearranges. There is no evidence of a 1,2-shift into the homocubyl system. Instead, one, two, or three bonds of the cubane nucleus cleave, leading to a variety of olefinic products. For the most part, these have been characterized. A mechanistic scheme accounting for their formation is presented; sequential sigma-bond breaking occurs regioselectively, favoring processes in which there is good overlap between the radical orbital and that of the breaking bond. The distribution of products is shown to depend qualitatively on the time the radical intermediates are let live, that is, on the concentration and effectiveness of the hydrogen atom transfer agent. From product distributions, the rate constant for ring cleavage of cubylcarbinyl radical is calculated to be at least 2 X 10(10) s-1, substantially greater than that of any radical derived to date from a saturated hydrocarbon system. Methodology is given for the synthesis of cubylcarbinol, cubylacetic acid, 1,4-bis(hydroxymethyl)cubane, methylcubane, and a variety of other new cubane compounds.

  DOI：

  10.1021/ja00020a035
• 作为产物：
  描述：

  甲基锂 、 1,4-二碘五环[4.2.0.02,5.03,8.04,7]辛烷 在 碘甲烷 作用下， 以 乙醚 为溶剂， 反应 4.5h， 以70%的产率得到4-methylcubane-1-iodide
  参考文献：
  名称：

  Synthesis of Methylcubane and Cyclopropylcubane. The Cubane-1,4-diyl Route

  摘要：

  Details for preparation of 1,4-diiodocubane from cubane-1,4-dicarboxylic acid are given. The diiodide is used to generate cubane-1,4-diyl, a nonisolable intermediate. Additions to the diyl are shown to provide for the ready synthesis in good yield of methylcubane, 1,4-dimethylcubane, cyclopropylcubane, etc.

  DOI：

  10.1021/jo00109a030

文献信息

• Rearrangement-Free Hydroxylation of Methylcubanes by a Cytochrome P450: The Case for Dynamical Coupling of C–H Abstraction and Rebound
  作者：Md. Raihan Sarkar、Sevan D. Houston、G. Paul Savage、Craig M. Williams、Elizabeth H. Krenske、Stephen G. Bell、James J. De Voss

  DOI：10.1021/jacs.9b08064

  日期：2019.12.18

  methylcubane oxidations which notionally proceed via cubylmethyl radical intermediates yet are remarkably free of rearrangement. The bacterial cytochrome P450 CYP101B1 from Novosphingobium aromaticivorans DSM 12444 is found to hydroxylate the methyl group of a range of methylcubane substrates containing a regio-directing carbonyl functionality at C-4. Unlike other reported P450-catalyzed methylcubane oxidations

  通过切断立方体的两个键，高度应变的立方甲基自由基经历了已知最快的自由基重排之一（据报道，在 25°C 下 k = 2.9 × 1010 s-1）。这种重排以前已被用作机械探针来检测酶催化 CH 氧化中基于自由基的途径。本文报道了高选择性细胞色素 P450 催化的甲基立方氧化的发现，其理论上通过立方甲基自由基中间体进行，但显着没有重排。发现来自新鞘氨醇 DSM 12444 的细菌细胞色素 P450 CYP101B1 可将一系列含有区域导向羰基官能团的甲基立方底物的甲基羟基化到 C-4。与其他报道的 P450 催化的甲基立方氧化不同，设计的甲基古巴烷以高效和选择性羟基化，产生高达 93% 的立方甲醇。立方环开环的缺乏意味着在这些 CYP101B1 催化的羟基化过程中形成的立方甲基自由基必须具有非常短的寿命，只有几皮秒，这对于它们来说太短，无法表现出完全平衡的 P450 中间体的副反应特征。我们
• The preparation and fate of cubylcarbinyl radicals
  作者：Philip E. Eaton、Yu Chi Yip

  DOI：10.1021/ja00020a035

  日期：1991.9

  The cubylcarbinyl radical has been generated from cubylcarbinyl bromide and from the N-hydroxy-2-pyridinethione ester of cubylacetic acid under various conditions favoring hydrogen-atom transfer to the radical. Only when selenophenol in high concentration is used as the hydrogen donor is any methylcubane formed. Otherwise the cubylcarbinyl radical rearranges. There is no evidence of a 1,2-shift into the homocubyl system. Instead, one, two, or three bonds of the cubane nucleus cleave, leading to a variety of olefinic products. For the most part, these have been characterized. A mechanistic scheme accounting for their formation is presented; sequential sigma-bond breaking occurs regioselectively, favoring processes in which there is good overlap between the radical orbital and that of the breaking bond. The distribution of products is shown to depend qualitatively on the time the radical intermediates are let live, that is, on the concentration and effectiveness of the hydrogen atom transfer agent. From product distributions, the rate constant for ring cleavage of cubylcarbinyl radical is calculated to be at least 2 X 10(10) s-1, substantially greater than that of any radical derived to date from a saturated hydrocarbon system. Methodology is given for the synthesis of cubylcarbinol, cubylacetic acid, 1,4-bis(hydroxymethyl)cubane, methylcubane, and a variety of other new cubane compounds.
• Solvolyses of cubyl triflates. The cubyl cation
  作者：Robert M. Moriarty、Sudersan M. Tuladhar、Raju Penmasta、Alok K. Awasthi

  DOI：10.1021/ja00164a063

  日期：1990.4
• Synthesis of Methylcubane and Cyclopropylcubane. The Cubane-1,4-diyl Route
  作者：Philip E. Eaton、Jianchang Li、Subhash P. Upadhyaya

  DOI：10.1021/jo00109a030

  日期：1995.2

  Details for preparation of 1,4-diiodocubane from cubane-1,4-dicarboxylic acid are given. The diiodide is used to generate cubane-1,4-diyl, a nonisolable intermediate. Additions to the diyl are shown to provide for the ready synthesis in good yield of methylcubane, 1,4-dimethylcubane, cyclopropylcubane, etc.