(μ-η2-1,10-bis(3',4',5'-trimethoxyphenyl)-2,8-decadiyne-1,10-diol)bis(dicobalt hexacarbonyl) | 1017295-60-1

• 英文名称: (μ-η2-1,10-bis(3',4',5'-trimethoxyphenyl)-2,8-decadiyne-1,10-diol)bis(dicobalt hexacarbonyl)
• CAS: 1017295-60-1
• 化学式: C₄₀H₃₄Co₄O₂₀
• 分子量: 1070.67
• InChiKey: PITRZLFFFOVOMG-KBUWWAFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (μ-η2-1,10-bis(3',4',5'-trimethoxyphenyl)-2,8-decadiyne-1,10-diol)bis(dicobalt hexacarbonyl) 、 tetrafluoroboric acid dimethyl ether complex 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Intramolecular Cyclizations of Co₂(CO)₆-Complexed Propargyl Radicals: Synthesis of d,l- and meso-1,5-Cyclodecadiynes

  摘要：

  Intramolecular radical cyclizations of Co-2(CO)(6)-complexed bis-propargyl alcohols 1-5 provide an easy, two-step access to the otherwise hardly accessible d,l- and meso-3,4-diaryl-1,5-cyclodecadiynes 21-25. The acid-induced generation of bis-cations 6-10 is followed by reduction with a 100-fold excess of zinc, generating key reactive intermediates, i.e. the cobalt-complexed bis-propargyl radicals 11-15. The substitution pattern (0-, 4-, 3,4-, 3,4,5-) and the nature of aromatic substituents (H, i-Pr, OMe) are found essential both to the diastereoselectivity of the process-with d,l:meso ratios varying from 54:46 to 80:20-and the isolability of individual stereoisomers. In particular, an accumulation of methoxy groups on the periphery of the aromatic rings facilitates separation in both intra- and intermolecular reactions. The observed disparity in the level of diastereoselection in intra- and intermolecular reactions is accounted for on the basis of conformational analysis, calculation data for cobalt-complexed propargyl radicals, and the concept of a CH/pi coordination. The new knowledge thus acquired has a predicting power, allowing future substrates to be designed, both topologically and stereoelectronically, in a manner favoring either d,l or meso diastereomers.

  DOI：

  10.1021/om7010497
• 作为产物：
  描述：

  dicobalt octacarbonyl 、 1,10-bis(3',4',5'-trimethoxyphenyl)-2,8-decadiyne-1,10-diol 以 乙醚 为溶剂， 以13.8%的产率得到(μ-η2-1,10-bis(3',4',5'-trimethoxyphenyl)-2,8-decadiyne-1,10-diol)bis(dicobalt hexacarbonyl)
  参考文献：
  名称：

  Intramolecular Cyclizations of Co₂(CO)₆-Complexed Propargyl Radicals: Synthesis of d,l- and meso-1,5-Cyclodecadiynes

  摘要：

  Intramolecular radical cyclizations of Co-2(CO)(6)-complexed bis-propargyl alcohols 1-5 provide an easy, two-step access to the otherwise hardly accessible d,l- and meso-3,4-diaryl-1,5-cyclodecadiynes 21-25. The acid-induced generation of bis-cations 6-10 is followed by reduction with a 100-fold excess of zinc, generating key reactive intermediates, i.e. the cobalt-complexed bis-propargyl radicals 11-15. The substitution pattern (0-, 4-, 3,4-, 3,4,5-) and the nature of aromatic substituents (H, i-Pr, OMe) are found essential both to the diastereoselectivity of the process-with d,l:meso ratios varying from 54:46 to 80:20-and the isolability of individual stereoisomers. In particular, an accumulation of methoxy groups on the periphery of the aromatic rings facilitates separation in both intra- and intermolecular reactions. The observed disparity in the level of diastereoselection in intra- and intermolecular reactions is accounted for on the basis of conformational analysis, calculation data for cobalt-complexed propargyl radicals, and the concept of a CH/pi coordination. The new knowledge thus acquired has a predicting power, allowing future substrates to be designed, both topologically and stereoelectronically, in a manner favoring either d,l or meso diastereomers.

  DOI：

  10.1021/om7010497