1-(4-methylbenzylidene)-1,3-dihydroisobenzofuran | 64421-13-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异香豆素
• 英文名称: 1-(4-methylbenzylidene)-1,3-dihydroisobenzofuran
• 英文别名: 3-[(4-methylphenyl)methylidene]-1H-2-benzofuran
• CAS: 64421-13-2
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: JWUKFZMHQGSDLS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(4-methylbenzylidene)-1,3-dihydroisobenzofuran 、 2-(三甲基硅)苯基三氟甲烷磺酸盐 在 cesium fluoride 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以71%的产率得到5a-phenyl-6-(p-tolyl)-5a,6-dihydro-4H-phenanthro[10,1-bc]furan
  参考文献：
  名称：

  苯乙炔与功能化亚苄基萘对Afford Phenanthro [10,1- bc ]呋喃的串联反应

  摘要：

  首次以中等至良好的产率实现了苯并炔与功能化的亚苄基萘的串联反应，以合成多种菲[10,1- bc ]呋喃。反应机理包括Diels-Alder反应和分子间亲核加成反应为关键步骤。

  DOI：

  10.1021/jo402701q
• 作为产物：
  描述：

  (2-(p-tolylethynyl)phenyl)methanol 在 C₃₄H₂₅AuClP 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 1-(4-methylbenzylidene)-1,3-dihydroisobenzofuran 、 3-(p-tolyl)-1H-isochromene
  参考文献：
  名称：

  三芳基类似物MONO-，BIS-和TRISKITPHOS膦：合成，溶液NMR研究以及在金催化的碳-杂原子键形成5-exo-dig和6-endo-dig环化反应中的比较

  摘要：

  A homologous series of triaryl-like KITPHOS-type monophosphines containing one, two, or three bulky 12-phenyl-9,10-dihydro-9,10-ethenoanthracene (KITPHOS) units have been developed, and the influence of increasing steric bulk on their efficacy as ligands in gold(I)-catalyzed carbon-heteroatom bond-forming cyclizations has been investigated. Detailed solution NMR studies on Ph-TRISKITPHOS, its oxide, and the corresponding gold(I) chloride adduct identified a conformational exchange process involving a concerted librational motion of the individual anthracene-derived organic substituents about their P-C bonds. The cessation of this motion at reduced temperatures lowers the molecular symmetry such that the two C6H4 rings in each of the KITPHOS units become inequivalent; a lower energy process involving restricted rotation of the biaryl-like phenyl ring has also been identified. Electrophilic gold(I) complexes of these triaryl-like KITPHOS monophosphines catalyze the 5-exo-dig cycloisomerization of propargyl amides to afford the corresponding methylene oxazolines, which were used in a subsequent tandem carbonyl-ene reaction to afford functionalized 2 -substituted oxazolines. A comparative survey revealed that catalyst efficiency for cycloisomerization decreases in the order MONOKITPHOS = BISKITPHOS > PPh3 > TRISKITPHOS. The optimum system also catalyzes the selective 6-endo-dig cyclization of 2-alkynylbenzyl alcohols, 2-alkynylbenzoic acid, and 2-phenylethynyl benzamides; gratifyingly, in several cases the yields obtained are markedly higher and/or reaction times significantly shorter than those previously reported for related gold catalysts. Moreover, these are the first examples of gold(I)-catalyzed 6-endo-dig cycloisomerizations involving 2-phenylethynyl benzamides and, reassuringly, the optimum gold(I)/MONOKITPHOS systems either rivaled or outperformed existing silver or palladium based catalysts. The steric parameters of this homologous series of phosphines have been quantified and compared with selected triarylphosphines using a combination of Solid -G calculations, to determine the percentage of the metal coordination sphere shielded by the phosphine (the G parameter), and Salerno molecular buried volume calculations (SambVca) to determine the percent buried volume (%V-bur); the corresponding Tolman cone angles have also been determined from correlations.

  DOI：

  10.1021/acs.organomet.6b00146