2-((allyloxy)methyl)thiophene | 79708-31-9

• 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-((allyloxy)methyl)thiophene
• 英文别名: Thiophene, 2-[(2-propenyloxy)methyl]-；2-(prop-2-enoxymethyl)thiophene
• CAS: 79708-31-9
• 化学式: C₈H₁₀OS
• 分子量: 154.233
• InChiKey: YRZGIPFLJGLYMV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  37.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-((allyloxy)methyl)thiophene 在 正丁基锂 作用下， 以 乙醚 为溶剂， 反应 1.5h， 以25%的产率得到1-(thiophen-2-yl)but-3-en-1-ol
  参考文献：
  名称：

  Anisimov, A. V.; Mozhaeva, L. V.; Viktorova, E. A., Journal of Organic Chemistry USSR (English Translation), 1981, p. 1387 - 1388

  摘要：

  DOI：
• 作为产物：
  描述：

  2-(1-allyloxy-allyl)thiophene 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以61.4%的产率得到2-((allyloxy)methyl)thiophene
  参考文献：
  名称：

  将有机铬试剂添加到杂芳基醛中。杂芳基取代的双烯丙基醚和高烯丙基醚的合成。

  摘要：

  用两种不同的方法合成了杂芳基取代的烯丙醇和高烯丙醇。双烯丙基醚和高烯丙基醚的合成分别通过烯丙基溴与烯丙醇和高烯丙基醇的反应进行。使用 GC/MS 技术研究了杂芳基取代的双烯丙基醚的 [2.3]-Wittig 重排反应。在这些反应中，以高产率分离出两种意想不到的产物。

  DOI：

  10.3390/90100022

文献信息

• Excited‐State Copper Catalysis for the Synthesis of Heterocycles
  作者：Arghya Banerjee、Satavisha Sarkar、Jagrut A. Shah、Nicoline C. Frederiks、Emmanuel A. Bazan‐Bergamino、Christopher J. Johnson、Ming‐Yu Ngai

  DOI：10.1002/anie.202113841

  日期：2022.1.21

  Visible-light-induced excited-state copper catalysis enables the synthesis of more than 10 distinct classes of heterocycles. The reaction tolerates a broad array of functional groups and complex molecular scaffolds, including derivatives of peptides, natural products, and marketed drugs.

  可见光诱导的激发态铜催化能够合成 10 多种不同类别的杂环化合物。该反应可耐受多种官能团和复杂的分子支架，包括肽衍生物、天然产物和市售药物。
• Asymmetric Allylic C–H Alkylation of Allyl Ethers with 2-Acylimidazoles
  作者：Tian-Ci Wang、Lian-Feng Fan、Yang Shen、Pu-Sheng Wang、Liu-Zhu Gong

  DOI：10.1021/jacs.9b05247

  日期：2019.7.10

  An asymmetric allylic C-H alkylation of allyl ethers has been established by chiral phosphoramidite-palladium catalysis, affording a wide variety of functionalized chiral 2-acylimidazoles in moderate to high yields and with high levels of enantioselectivity. Moreover, this protocol could be applied to a concise asymmetric synthesis of a tachykinin receptor antagonist.

  通过手性亚磷酰胺-钯催化建立了烯丙基醚的不对称烯丙基 CH 烷基化，以中等至高产率和高水平对映选择性提供各种功能化的手性 2-酰基咪唑。此外，该协议可应用于速激肽受体拮抗剂的简明不对称合成。
• Selective zirconocene hydride-catalyzed semi-hydrogenation of terminal alkynes
  作者：Rebecca A. Kehner、Alexandra E. Lubaev、Manjula D. Rathnayake、Ryan Loden、Ge Zhang、Liela Bayeh-Romero

  DOI：10.1016/j.tet.2023.133267

  日期：2023.3

  in the area of zirconocene hydride catalysis, we have identified a mild and chemoselective strategy for the formal semi-hydrogenation of terminal alkynes utilizing catalytic quantities of Schwartz's reagent or Cp2ZrCl2. This protocol accommodates a variety of functional groups, delivering monosubstituted alkenes bearing ester, nitrile, epoxy, amino, halo, sulfide and hydroxyl groups.

  基于我们最近在茂锆氢化物催化领域的发现，我们已经确定了一种温和的化学选择性策略，用于利用催化量的 Schwartz 试剂或 Cp 2 ZrCl 2 对末端炔烃进行形式半氢化。该协议适用于各种官能团，提供带有酯、腈、环氧、氨基、卤素、硫化物和羟基的单取代烯烃。
• Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals
  作者：Laura Capella、Pier Carlo Montevecchi、Maria Luisa Navacchia

  DOI：10.1021/jo00128a013

  日期：1995.11

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.
• Wittig Rearrangement of Ally 2-Thiophenemethyl Ethers: Facile Synthesis of Thiophenemethanol and -ethanol Derivatives
  作者：Masayoshi Tsubuki、Toshio Honda、Sohichiro Matsuo

  DOI：10.3987/com-05-s(k)5

  日期：——

  Wittig rearrangement of allyl 2-thiophenemethyl ethers was studied. Deprotonation of allyl 2-thiophenemethyl ethers (1a-d) occurred preferentially either the alpha- or the alpha'-position, depending on three kinds of BuLi. Thiophenemethanol and -ethanol derivatives were obtained as products of [2,31 and [1,2] sigmatropic rearrangements, respectively.