3-phenyl-7-(4-vinylphenyl)hepta-1,6-diyn-3-yl benzoate | 1435518-46-9

• 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: 3-phenyl-7-(4-vinylphenyl)hepta-1,6-diyn-3-yl benzoate
• CAS: 1435518-46-9
• 化学式: C₂₈H₂₂O₂
• 分子量: 390.481
• InChiKey: BPLHZTLKWPXEMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.85
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-phenyl-7-(4-vinylphenyl)hepta-1,6-diyn-3-yl benzoate 在 (acetonitrile)[(2',4',6'-triisopropyl-3,4,5,6-tetramethyl-1,1'-biphenyl-2-yl)di-tert-butylphosphine]gold(I) hexafluoroantimonate 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 以47%的产率得到3-phenyl-6-vinyl-2,4a-dihydro-1H-fluoren-4-yl benzoate
  参考文献：
  名称：

  Gold-Catalyzed Cycloisomerization of 1,6-Diyne Carbonates and Esters to 2,4a-Dihydro-1H-fluorenes

  摘要：

  A synthetic method to prepare 2,4a-dihydro-1H-fluorenes efficiently from gold(I)-catalyzed 1,2-acyloxy migration/cyclopropenation/Nazarov cyclization of 1,6-diyne carbonates and esters is described. The suggested reaction pathway provides rare examples of [2,3]-sigmatropic rearrangement in this class of compounds as well as the involvement of an in situ formed cyclopropene intermediate in gold catalysis. Experimental and ONIOM(QM:QM') [our own n-layered integrated molecular orbital and molecular mechanics(quantum mechanics quantum mechanics')] computational studies based on the proposed Au carbenoid species provide insight into this unique selectivity.

  DOI：

  10.1021/ja4032727
• 作为产物：
  描述：

  在 N-甲基吗啉 、 正丁基锂 、 N,N'-二环己基碳二亚胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 环己烷 为溶剂， 反应 22.83h， 生成 3-phenyl-7-(4-vinylphenyl)hepta-1,6-diyn-3-yl benzoate
  参考文献：
  名称：

  Gold-Catalyzed Cycloisomerization of 1,6-Diyne Carbonates and Esters to 2,4a-Dihydro-1H-fluorenes

  摘要：

  A synthetic method to prepare 2,4a-dihydro-1H-fluorenes efficiently from gold(I)-catalyzed 1,2-acyloxy migration/cyclopropenation/Nazarov cyclization of 1,6-diyne carbonates and esters is described. The suggested reaction pathway provides rare examples of [2,3]-sigmatropic rearrangement in this class of compounds as well as the involvement of an in situ formed cyclopropene intermediate in gold catalysis. Experimental and ONIOM(QM:QM') [our own n-layered integrated molecular orbital and molecular mechanics(quantum mechanics quantum mechanics')] computational studies based on the proposed Au carbenoid species provide insight into this unique selectivity.

  DOI：

  10.1021/ja4032727

文献信息

• Gold-Catalyzed [2+2+1] Cycloaddition of 1,6-Diyne Carbonates and Esters with Aldehydes to 4-(Cyclohexa-1,3-dienyl)-1,3-dioxolanes
  作者：Weidong Rao、Philip Wai Hong Chan

  DOI：10.1002/chem.201303685

  日期：2014.1.13

  gold(I)‐catalyzed [2+2+1] cycloaddition of 1,6‐diyne carbonates and esters with aldehydes is described. The cascade process involves 1,2‐acyloxy migration followed by cyclopropenation and cycloreversion. This leads to an unprecedented [2+2+1] cycloaddition of the resulting alkenylgold carbenoid species, examples of which are extremely rare, with two aldehyde molecules at catalyst loadings as low as 1 mol %. The

  一种金（I）催化的[2 + 2 + 1]环加成碳酸1,6-二炔碳酸酯的立体选择性立体合成4-（环己-1,3-二烯基）-1,3-二氧戊环的合成方法描述了与醛的酯。级联过程涉及1,2-酰氧基迁移，然后进行环丙烷化和环还原。这导致所得到的烯基金类胡萝卜素物质发生前所未有的[2 + 2 + 1]环加成反应，其例子极为罕见，其中两个醛分子的催化剂负载量低至1 mol％。通过将一个实施例转化为相应的苯酚，进一步证明了这种环异构化化学的有用性。