2-(2-iodoethyl)thiophene | 92138-63-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 2-(2-iodoethyl)thiophene
• 英文别名: 1-iodo-2-(thien-2-yl)ethane
• CAS: 92138-63-1
• 化学式: C₆H₇IS
• 分子量: 238.092
• InChiKey: QDGRUDZEGWMJOB-UHFFFAOYSA-N

物化性质

• 沸点：
  242.1±23.0 °C(Predicted)
• 密度：
  1.823±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(2-iodoethyl)thiophene 在 六甲基磷酰三胺 、 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 20.5h， 生成 dimethyl 2-[5-(thiophen-2-yl)pent-1-en-3-yl]malonate
  参考文献：
  名称：

  烯丙基4-氯苯基砜作为通用的1,1-合成子，可顺序进行α-烷基化/钴催化的烯丙基取代

  摘要：

  尽管烯丙基砜具有罕见的1,1-偶极合成子的独特潜力，但很少用于目标导向的合成中，这可能是由于缺乏用于支链选择性烯丙基取代的通用催化方法。在这里，我们确定了烯丙基4-氯苯基砜作为通用介导的碱介导的α-衍生化和随后的钴催化的烯丙基取代。连续转化允许高度区域选择性地获得具有多种脂族侧链的支链烯丙基取代产物。与传统的金属催化方案相比，光氧化还原使能的钴催化对于实现高产率和区域选择性的脱磺酰基取代是必不可少的，而传统的金属催化方案在相应的转化中导致了较差的结果。

  DOI：

  10.1055/s-0040-1707524
• 作为产物：
  描述：

  2-噻吩乙酸 在 咪唑 、 dimethyl sulfide borane 、 三苯基膦二碘化物 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 2-(2-iodoethyl)thiophene
  参考文献：
  名称：

  2-Substituted (2SR)-2-Amino-2-((1SR,2SR)-2-carboxycycloprop-1-yl)glycines as Potent and Selective Antagonists of Group II Metabotropic Glutamate Receptors. 1. Effects of Alkyl, Arylalkyl, and Diarylalkyl Substitution

  摘要：

  In this paper, we describe the synthesis of a series of a-substituted analogues of the potent and selective group II metabotropic glutamate receptor (mGluR) agonist (1S,1'S,2'S)-carboxy-cyclopropylglycine (2, L-CCG 1). Incorporation of a substituent on the amino acid carbon converted the agonist 2 into antagonist. Ail of the compounds were prepared and tested as a series of four isomers, i.e., two racemic diastereomers. We explored alkyl substitution, both normal and terminally branched; phenylalkyl and diphenylalkyl substitution; and a variety of aromatic and carbocyclic surrogates for phenyl. Affinity for group II mGluRs was measured using [H-3]glutamic acid (Glu) binding in rat forebrain membranes. Antagonist activity was confirmed for these compounds by measuring their ability to antagonize (1S,3R)-1-aminocyclopentane-1,3-dicarboxylic acid-induced inhibition of forskolin-stimulated cyclic-AMP in RGT cells transfected with human mGluR2 and mGluR3. We found that while alkyl substitution provided no increase in affinity relative to 2, phenylethyl and diphenylethyl substitution, as in 105 and 109, respectively, were quite beneficial, The affinity of 109 was further enhanced when the two aromatic rings were joined by an oxygen or sulfur atom to form the tricyclic xanthylmethyl and thioxanthylmethyl amino acids 113 and 114, respectively. Amino acid 113, with an IC50 of 0.10 mu M in the [H-3]Glu binding assay, was 52-fold more patent than 2, whose IC50 was 0.47 mu M.

  DOI：

  10.1021/jm970497w

文献信息

• Transition metal- and light-free radical borylation of alkyl bromides and iodides using silane
  作者：Beiqi Sun、Sihan Zheng、Fanyang Mo

  DOI：10.1039/d1cc02134f

  日期：——

  for borylation of alkyl bromides and iodides to alkyl boronic esters under transition metal- and light-free conditions. A series of substrates with a wide range of functional groups were effectively transformed into the borylation products in moderate to good yields. Mechanistic studies, including radical clock experiments and DFT calculations, gave detailed insight into the radical borylation process

  我们报告了在无过渡金属和无光条件下将烷基溴和碘化物硼化为烷基硼酸酯的操作简单和中性的条件。一系列具有广泛功能基团的底物以中等到良好的产率有效地转化为硼酸酯化产物。包括自由基时钟实验和DFT计算在内的机理研究，使人们对自由基硼化过程有了更深入的了解。
• Migratory Hydrogenation of Terminal Alkynes by Base/Cobalt Relay Catalysis
  作者：Xufang Liu、Bingxue Liu、Qiang Liu

  DOI：10.1002/anie.201916014

  日期：2020.4.20

  an analogous protocol for alkyne substrates is yet to be developed. Herein, a base and cobalt relay catalytic process for the selective synthesis of (Z)-2-alkenes and conjugated E alkenes by migratory hydrogenation of terminal alkynes is disclosed. Mechanistic studies support a relay catalytic process involving a sequential base-catalyzed isomerization of terminal alkynes and cobalt-catalyzed hydrogenation

  烯烃的迁移功能化已成为一种强大的策略，可在烃链上原始反应位点的远侧位置实现功能化。但是，尚未开发出用于炔烃底物的类似方案。本文中，公开了通过末端炔的迁移加氢选择性合成（Z）-2-烯烃和共轭E烯烃的碱和钴中继催化方法。机理研究支持中继催化过程，该过程涉及末端炔烃的顺序碱催化异构化和2-炔烃或共轭二烯中间体的钴催化氢化。值得注意的是，这种实用的非贵金属催化系统能够有效控制这种转化的化学，区域和立体选择性。
• Ligand‐Controlled Regiodivergent Hydroalkylation of Pyrrolines
  作者：Deyun Qian、Xile Hu

  DOI：10.1002/anie.201912629

  日期：2019.12.16

  Nickel hydride (NiH) catalyzed hydrocarbonation has emerged as an efficient approach to construct new C-C bonds containing at least one C(sp3 ) center. However, the regioselectivity of this reaction is by far dictated by substrates. Described here is a strategy to achieve two different regioselectivites of hydroalkylation of the same substrates by using ligand control. This strategy enables the first

  氢化镍（NiH）催化的碳氢化合物已成为一种有效的构建含有至少一个C（sp3）中心的新CC键的方法。但是，该反应的区域选择性到目前为止受底物支配。这里描述的是通过使用配体控制来实现相同底物的两种不同的区域选择性加氢烷基化烷基化的策略。这种策略使3-吡咯啉能够进行第一次区域发散性加氢烷基化，从而在许多生物活性分子中产生2-和3-烷基化的吡咯烷，有价值的合成中间体和常见基序。该方法显示了广泛的范围和较高的官能团耐受性，可用于后期功能化。
• Synthesis of <i>E</i>-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes
  作者：Thomas Di Franco、Alexandre Epenoy、Xile Hu

  DOI：10.1021/acs.orglett.5b02482

  日期：2015.10.2

  The first Ni-catalyzed Suzuki–Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal alkynes, allowing the expedited synthesis of functionalized alkyl alkenes from readily available alkynes with complete (E)-selectivity in one pot

  据报道，烷基卤化物与烯基-（9-BBN）试剂的首次Ni催化的Suzuki-Miyaura偶联反应。包括烷基氯化物的伯烷基卤和仲烷基卤都可以偶联。该偶联方法可以与末端炔烃的硼氢化反应结合使用，从而允许在一个反应​​釜中从容易获得的炔烃以完全的（E）选择性加速合成官能化的烷基烯烃。该方法用于天然大环内酯（±）-瑞奇奥利特的全合成。
• Nickel‐Catalyzed Regioselective Hydroalkylation and Hydroarylation of Alkenyl Boronic Esters
  作者：Srikrishna Bera、Xile Hu

  DOI：10.1002/anie.201907045

  日期：2019.9.23

  catalyzed hydrocarbonation, linear selectivity is most often obtained because of the relative stability of the linear Ni-alkyl intermediate over its branched counterpart. Herein, we show that the boronic pinacol ester (Bpin) group directs a Ni-catalyzed hydrocarbonation to occur at its adjacent carbon center, resulting in formal branch selectivity. Both alkyl and aryl halides can be used as electrophiles

  金属氢化物催化烯烃的烃化反应是从容易获得的烯烃中构建新的碳-碳键的有效方法。然而，烃化的区域选择性仍然难以控制。在氢化镍（NiH）催化的烃化反应中，由于线性Ni-烷基中间体相对于其支链对应物的相对稳定性，最经常获得线性选择性。在这里，我们显示硼烷频哪醇酯（Bpin）基团指导Ni催化的烃化反应发生在其相邻的碳中心，从而形成正式的分支选择性。烷基卤化物和芳基卤化物均可在此烃化反应中用作亲电子试剂，从而提供了广泛的仲烷基Bpin衍生物的途径，它们是合成化学中的重要组成部分。