3-(4-chlorophenyl)-7-phenyl-1-(trimethylsilyl)hepta-1,6-diyn-3-ol | 1435518-31-2

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: 3-(4-chlorophenyl)-7-phenyl-1-(trimethylsilyl)hepta-1,6-diyn-3-ol
• CAS: 1435518-31-2
• 化学式: C₂₂H₂₃ClOSi
• 分子量: 366.963
• InChiKey: USVIVPMMFYYAAP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-(4-chlorophenyl)-7-phenyl-1-(trimethylsilyl)hepta-1,6-diyn-3-ol 在 (acetonitrile)[(2',4',6'-triisopropyl-3,4,5,6-tetramethyl-1,1'-biphenyl-2-yl)di-tert-butylphosphine]gold(I) hexafluoroantimonate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.83h， 生成 3-(4-chlorophenyl)-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：

  methyl 5-phenylpent-4-ynoate 在 N-甲基吗啉 、 正丁基锂 、 N,N'-二环己基碳二亚胺 、 potassium hydroxide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 、 环己烷 、 水 为溶剂， 反应 21.0h， 生成 3-(4-chlorophenyl)-7-phenyl-1-(trimethylsilyl)hepta-1,6-diyn-3-ol
  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