6-phenyl-5-hexyn-1-mesylate | 936501-77-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 6-phenyl-5-hexyn-1-mesylate
• CAS: 936501-77-8
• 化学式: C₁₃H₁₆O₃S
• 分子量: 252.334
• InChiKey: JSWSYICFYWJNAM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.18
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  6-phenyl-5-hexyn-1-mesylate 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (6-azidohex-1-yn-1-yl)benzene
  参考文献：
  名称：

  衍生的2-硝基-1,1-乙二胺的酸介导的分子内1,3-偶极环加成反应，用于合成新型稠合双环异恶唑

  摘要：

  发现了一种新的新型稠合双环异恶唑的合成方法，例如，N-甲基-3-苯基-5,6-二氢-4 H-异恶唑并[3,4- c ]氮杂8-胺（2a），N -甲基-3-苯基-4,5-二氢异恶唑[3,4- c ]吡啶-7-胺（2b）和N-甲基-3-苯基-4 H-吡咯并[3,4- c ]异恶唑-6报道了高产率的-胺（2d）。我们推测反应是通过酸介导的分子内1，3-偶极环加成反应从2-硝基-1,1-乙二胺1a，b，d进行的。

  DOI：

  10.1016/j.tetlet.2010.04.098
• 作为产物：
  描述：

  5-己炔-1-醇 在 copper(l) iodide 、 四(三苯基膦)钯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 生成 6-phenyl-5-hexyn-1-mesylate
  参考文献：
  名称：

  Intramolecular Hydroamination of Alkynes Catalyzed by Pd(PPh₃)₄/Triphenylphosphine under Neutral Conditions

  摘要：

  The intramolecular hydroamination of alkynes tethered with amino group 1 in the presence of catalytic amounts of Pd(PPh3)(4) and PPh3 in benzene at 100 degrees C proceeded smoothly without the use of any additional acid source to afford five and six-membered nitrogen heterocycles 2 in good to excellent yields. A compulsory addition of carboxylic acid as a cocatalyst was not needed, and the reaction could be carried out under essentially neutral conditions.

  DOI：

  10.1021/jo050412w

文献信息

• Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation
  作者：Bryan D. Stubbert、Tobin J. Marks

  DOI：10.1021/ja0665444

  日期：2007.4.1

  A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)(2) (CGC = Me2Si(eta(5)-Me4C5)((BuN)-Bu-t); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl-2, 2-Cl-2) and slightly more soluble diiodides (1-I-2, 2-I-2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp ''(2)AnR(2) (Cp '' = eta(5)-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'(2)AnR(2) (Cp' = eta(5)-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N-t up to 3000 h(-1)) and high regioselectivities (>= 95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting CC/CC insertion into the An-N sigma-bond.