6-iodo-6-methyl-1-heptene | 109422-82-4

• 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: 6-iodo-6-methyl-1-heptene
• 英文别名: 6-iodo-6-methylhept-1-ene
• CAS: 109422-82-4
• 化学式: C₈H₁₅I
• 分子量: 238.112
• InChiKey: VQSKQXBOROFXGH-UHFFFAOYSA-N

物化性质

• 沸点：
  200.3±19.0 °C(Predicted)
• 密度：
  1.364±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  6-iodo-6-methyl-1-heptene 在 水 、 三正丁基氢锡 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 2.5h， 生成 2-hydroxymethyl-2-[(2-methyl-1-phenylpropyl)(1,1-dimethylhex-5-enyloxy)amino]propane-1,3-diol
  参考文献：
  名称：

  影响烷氧基胺的CO键均质化的因素：氢键和极性取代基的影响。

  摘要：

  描述了各种新的三烷基羟胺的合成。已经测量了这些新的烷氧基胺的CO键裂解的速率常数。例如，一系列对位取代的TEMPO-苯乙烯基化合物TEMPO-CH（CH3）C6H5X 1a（p-MeO），1b（p-Me），1d（pH），1e（p-Br）的CO键均质速率，并显示1f（p-MeO2C）。此外，讨论了α-杂芳基取代的仲烷氧基胺的CO键裂解的速率常数。提出了一种相关性，通过该相关性，可以从相应烷烃的CH BDE预测TEMPO衍生的烷氧基胺的CO键裂解速率常数。讨论了溶剂效应以及樟脑磺酸对CO键均质分解速率的影响。最后，

  DOI：

  10.1021/jo001190z
• 作为产物：
  描述：

  5-溴-1-戊烯 在 四碘化二磷 、 magnesium 作用下， 以 二硫化碳 、 乙醚 为溶剂， 反应 5.67h， 生成 6-iodo-6-methyl-1-heptene
  参考文献：
  名称：

  自由基催化中的铋化合物：过渡金属铋有助于热诱导的环异构化。

  摘要：

  铋化合物的受控自由基化学仍处于起步阶段。这些配合物的特性（例如低毒性，高官能团耐受性，低均裂键解离能和可逆均裂键解离）为进一步的发展提供了动力，这些特性在合成化学中的应用极具吸引力。在这里，我们报道了过渡金属双变色烷（即具有Bi-TM键的化合物； TM =过渡金属）的首次催化应用。使用δ-碘代烯烃的催化自由基环异构化作为模型反应，证明了与已知的B，Mn，Cu，Zn，Sn和碱金属试剂互补或优于的特性（包括不同的关键中间体），建立了过渡金属双变黄烷作为控制自由基反应的一类新的（预）催化剂。

  DOI：

  10.1002/anie.201904365

文献信息

• Atom transfer cyclization of simple hexenyl iodides. A caution on the use of alkenyl iodides as probes for the detection of single electron transfer processes
  作者：Dennis P. Curran、Dooseop Kim

  DOI：10.1016/s0040-4039(00)85336-8

  日期：1986.1

  The trialkyltin initiated isomerization of 1-iodo-5-hexene to (iodomethyl)cyclopentane is reported. Rapid and reversible iodine atom transfer between alkyl radicals is the key chain transfer step. The results suggest an important caution in the use of hexenyl iodides as SET probes: a good mechanism exists whereby the yield of rearranged products may be much greater than the amount of radicals produced

  据报道，由三烷基锡引发的1-碘-5-己烯异构化为（碘甲基）环戊烷。烷基之间的快速和可逆的碘原子转移是关键的链转移步骤。结果表明，在使用己烯基碘化物作为SET探针时要特别小心：存在良好的机制，重排产物的产率可能比研究中的反应产生的自由基要大得多！
• Nickel-Catalyzed Reductive Dicarbofunctionalization of Alkenes
  作者：Andrés García-Domínguez、Zhaodong Li、Cristina Nevado

  DOI：10.1021/jacs.7b03195

  日期：2017.5.24

  An intermolecular, three-component reductive dicarbofunctionalization of alkenes is presented here. The combination of Ni catalysis with TDAE as final reductant enables the direct formation of Csp3-Csp3 and Csp3-Csp2 bonds across a variety of π-systems using two different electrophiles that are sequentially activated with exquisite selectivity under mild reaction conditions.

  本文介绍了烯烃的分子间、三组分还原性双碳官能化。Ni 催化与作为最终还原剂的 TDAE 相结合，可以使用两种不同的亲电子试剂在各种 π 系统中直接形成 Csp3-Csp3 和 Csp3-Csp2 键，这些亲电子试剂在温和的反应条件下以极好的选择性顺序活化。
• Reactions of Saturated and Unsaturated Tertiary Alkyl Halides and Saturated Secondary Alkyl Iodides with Lithium Aluminum Deuteride. Convincing Evidence for a Single-Electron-Transfer Pathway
  作者：E. C. Ashby、Catherine O. Welder

  DOI：10.1021/jo9807058

  日期：1998.10.1

  Reactions of saturated secondary and tertiary alkyl halides with LiAlH4 (LAH) and LiAlD4 (LAD) have been carried out, and convincing evidence for a single-electron-transfer (SET) pathway has been obtained. Reactions involving saturated alkyl halides with LAD provide a model system in which a halogen-atom radical chain process is not possible, and therefore, the observation of large quantities tin some cases >90%) of protium in the reduction product provides strong evidence for a radical intermediate and a SET pathway. Specifically, the reaction of 2-iodooctane (10) with LAD produced octane with a deuterium content as low as 21%. Also, the reaction of the tertiary halide 2-iodo-2-methylheptane (15) with LAD produced 2-methylheptane (16) with a deuterium content as low as 8%. The effect of stoichiometry, halogen type, and reaction vessel surface on these reactions was studied. Reaction of the unsaturated tertiary halide 6-iodo-6-methyl-1-heptene (25) with LAD was also studied and was found to proceed predominantly by a SET process involving a halogen-atom radical chain process. The possibility of a carbocation intermediate in all of these reactions is discussed.
• Catalytic Cycloisomerization of Unsaturated Organoiodides
  作者：William F. Bailey、Matthew W. Carson

  DOI：10.1021/jo981991q

  日期：1998.12.1

  Catalytic quantities of phenyllithium (PhLi) have been found to initiate novel 5-exo cycloisomerization of a variety of structurally diverse unsaturated organoiodides. The isomerization reaction appears to be a process of broad synthetic utility for the preparation of iodomethyl-substituted five-membered rings. Primary, secondary, tertiary, or aryl iodides tethered to a suitably positioned carbon-carbon pi-bond are converted cleanly to their cyclic isomers in good to excellent yield (i.e., 70-90%) by simply allowing a hydrocarbon-MTBE solution of the iodide to stand in the presence of a small quantity of PhLi at an appropriate temperature. The mechanism of the cycloisomerization was found to be substrate dependent: unsaturated aryl and primary alkyl iodides undergo isomerization via a three-step cascade (eqs 1-3) mediated by two reversible lithium-iodine exchange reactions bracketing an irreversible 5-exo cyclization of an unsaturated organolithium; unsaturated secondary and tertiary alkyl iodides apparently isomerize via a radical-mediated atom transfer process initiated by homolytic fragmentation of the ate-complex generated upon attack of PhLi on the iodine atom of the substrate.
• CURRAN D. P.; KIM DOOSEOP, TETRAHEDRON LETT., 27,(1986) N 48, 5821-5824
  作者：CURRAN D. P.、 KIM DOOSEOP

  DOI：——

  日期：——