1-azido-3-iodobicyclo[1.1.1]pentane | 136863-38-2

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 1-azido-3-iodobicyclo[1.1.1]pentane
• CAS: 136863-38-2
• 化学式: C₅H₆IN₃
• 分子量: 235.027
• InChiKey: WXJMMSCEXLNMMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  14.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-azido-3-iodobicyclo[1.1.1]pentane 在 lithium aluminium tetrahydride 、 盐酸 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 24.0h， 以86%的产率得到3-chloro-3-methylbutylamine hydrochloride
  参考文献：
  名称：

  用氢化铝锂还原3-碘代双环[1.1.1]戊基叠氮化物的重排：中间体的机理证据。

  摘要：

  DOI：

  10.1021/jo001510e
• 作为产物：
  描述：

  1,3-二碘双环[1.1.1]戊烷 在 sodium azide 、 sodium methylate 作用下， 以79%的产率得到1-azido-3-iodobicyclo[1.1.1]pentane
  参考文献：
  名称：

  用于点击化学的双环 [1.1.1] 戊烷衍生结构单元

  摘要：

  描述了双环 [1.1.1] 戊烷衍生的叠氮化物和末端炔烃（点击反应的有趣底物）的合成。除了少数例外，标题化合物是从常见的合成中间体 - 相应的羧酸开始，分两步或三步制备的。1-叠氮双环[1.1.1]戊烷合成的关键步骤是铜催化的重氮转移反应与咪唑-1-磺酰叠氮化物。双环[1.1.1] 戊基取代炔烃的制备依赖于 Seyferth-Gilbert 与 1-重氮-2-氧代丙基-膦酸二甲酯（Ohira-Bestmann 试剂）的同系化。结果表明，这两种类型的目标化合物都是点击反应的合适底物，因此它们是医药、组合和生物共轭化学的有前途的基石。

  DOI：

  10.1002/ejoc.201701296

文献信息

• [EN] BICYCLIC COMPOUNDS AS KINASE MODULATORS, METHODS AND USES THEREOF<br/>[FR] COMPOSÉS BICYCLIQUES UTILISÉS EN TANT QUE MODULATEURS DE KINASE, PROCÉDÉS ET UTILISATIONS DE CEUX-CI
  申请人：AGENCY SCIENCE TECH & RES

  公开号：WO2020027723A1

  公开（公告）日：2020-02-06

  The present disclosure relates to derivatives of bicyclic compounds and their uses in therapy. In particular, the present disclosure relates to derivatives of bicyclic compounds for use in modulating kinase enzymatic activity and accordingly modulating kinase-dependent diseases and conditions such as cancer and in specific embodiments, hepatocellular carcinoma (HCC). The present disclosure also relates to methods of synthesizing these compounds.

  本公开涉及双环化合物的衍生物及其在治疗中的用途。具体来说，本公开涉及双环化合物的衍生物，用于调节激酶酶活性，从而调节激酶依赖性疾病和情况，如癌症，特别是肝细胞癌（HCC）。本公开还涉及合成这些化合物的方法。
• Investigation of the Reactivity of 1-Azido-3-iodobicyclo[1.1.1]pentane under “Click” Reaction Conditions
  作者：Elisabeth Sitte、Brendan Twamley、Nitika Grover、Mathias O. Senge

  DOI：10.1021/acs.joc.0c02432

  日期：2021.1.1

  1]pentane (BCP) unit is under scrutiny as a bioisostere in drug molecules. We employed methodologies for the synthesis of different BCP triazole building blocks from one precursor, 1-azido-3-iodobicyclo[1.1.1]pentane, by “click” reactions and integrated cycloaddition–Sonogashira coupling reactions. Thereby, we accessed 1,4-disubstituted triazoles, 5-iodo-1,4,5-trisubstituted triazoles, and 5-alkynylated

  双环[1.1.1]戊烷（BCP）单元作为药物分子中的生物等排物正在接受审查。我们通过“点击”反应和集成的环加成－Sonogashira偶联反应，采用一种方法从一种前体1-叠氮基-3-碘代双环[1.1.1]戊烷合成不同的BCP三唑结构单元。因此，我们获得了1,4-二取代三唑，5-碘-1,4,5-三取代三唑和5-炔基化1,4,5-三取代三唑。这为在模块或一锅法基础上合成多取代的BCP三唑提供了条件。这些方法被进一步用于将卟啉部分附加到BCP核心上。
• A New Route to Bicyclo[1.1.1]pentan-1-amine from 1-Azido-3-iodobicyclo[1.1.1]pentane
  作者：Yi Ling Goh、Eric K.W. Tam、Paul H. Bernardo、Choon Boon Cheong、Charles W. Johannes、Anthony D. William、Vikrant A. Adsool

  DOI：10.1021/ol500635p

  日期：2014.4.4

  From a medicinal chemistry perspective, bicyclo[1.1.1]pentan-1-amine (1) has served as a unique and important moiety. Synthetically, however, this compound has received little attention, and only one scalable route to this amine has been demonstrated. Reduction of an easily available and potentially versatile intermediate, 1-azido-3-iodobicyclo[1.1.1]pentane (2), can offer both a flexible and scalable

  从药物化学的观点来看，双环[1.1.1]戊丹-1-胺（1）已经用作独特且重要的部分。但是，从合成上讲，该化合物几乎没有受到关注，并且仅证明了一种可扩展的途径来制备该胺。减少易获得且可能通用的中间体1-azido-3-iodobicyclo [1.1.1]戊烷（2），可以为该目标提供灵活且可扩展的替代方案。在这里，我们描述了我们对这种难以捉摸的转变的审查，并报告了我们在这项努力中取得的成功。
• 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.
• Scalable Synthesis of 1-Bicyclo[1.1.1]pentylamine via a Hydrohydrazination Reaction
  作者：Kevin D. Bunker、Neal W. Sach、Qinhua Huang、Paul F. Richardson

  DOI：10.1021/ol201883z

  日期：2011.9.2

  The reaction of [1.1.1]propellane with di-tert-butyl azodicarboxylate and phenylsliane In the presence of Mn(dpm)(3) to give di-tert-butyl 1-(bicyclo[1.1.1]pentan-1-yl)hydrazine-1,2-dicarboxylate Is described. Subsequent deprotection gives 1-bicyclo[1.1.1]pentylhydrazine followed by reduction to give 1-bicyclo[1.1.1]pentylamine. The reported route marks a significant improvement over the previous syntheses of 1-bicyclo[1.1.1]pentylamine In terms of scalability, yield, safety, and cost.