2,3-diphenyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-one | 41577-62-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,3-diphenyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-one
• 英文别名: 4,5-diphenyltricyclo[5.2.1.02,6]deca-4,8-dien-3-one
• CAS: 41577-62-2
• 化学式: C₂₂H₁₈O
• 分子量: 298.384
• InChiKey: GDIAVGGBFJFEFO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2,3-diphenyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-one 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 1,2,3-triphenylcyclopentadiene
  参考文献：
  名称：

  Generation of Cyclopentadienyl Ligands via the Pauson-Khand and Retro-Diels-Alder Reactions

  摘要：

  DOI：

  10.1021/ja00084a074
• 作为产物：
  描述：

  一氧化碳 、 2,5-Norbornadiene 、 二苯基乙炔 在 C₂₈H₂₁Co₂O₇P 作用下， 以 甲苯 为溶剂， 生成 2,3-diphenyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-one
  参考文献：
  名称：

  QuinoxP *（CO）4-μ-炔烃双钴配合物的合成，配位研究和催化Pauson-Khand反应

  摘要：

  The coordination of the P-stereogenic and sterically demanding bisphosphine QuinoxP* to mu-alkyne dicobalt hexacarbonyl complexes was studied experimentally and computationally. 'Whereas the coordination occurred exclusively in a chelating fashion, the diastereoselectivity was highly substrate dependent. However, it could be explained from the computed structure and energies of the different coordination modes. The fluxional behavior of these complexes was also studied computationally. Their performance as catalysts for the Pauson-Khand reaction was explored, and outstanding reactivity was observed. Although the asymmetric induction was low to "moderate, the stereochemical outcome could be mechanistically rationalized. This report provides promising results in terms of reactivity and mechanistic understanding for further developments of highly active chiral catalysts for intermolecular Pauson Khand reactions.

  DOI：

  10.1021/acs.organomet.7b00018

文献信息

• Heterobimetallic alkyne complexes in organic synthesis: An asymmetric variant of the Pauson-Khand reaction
  作者：David T. Rutherford、Steven D.R. Christie

  DOI：10.1016/s0040-4039(98)02178-9

  日期：1998.12

  The use of heterobimetallic alkyne complexes for the synthesis of cyclopentenones is described. The inherent chirality of the complexes has been used to effect high levels of stereocontrol in transformations giving optically enriched organic end products. (C) 1998 Elsevier Science Ltd. All rights reserved.