(μ-η²-4,4-dimethylpent-1-yn-3-ol)dicobalt hexacarbonyl | 109530-33-8

• 英文名称: (μ-η²-4,4-dimethylpent-1-yn-3-ol)dicobalt hexacarbonyl
• 英文别名: 2,2-dimethyl-4-pentyn-3-ol-dicobalt hexacarbonyl
• CAS: 109530-33-8
• 化学式: C₁₃H₁₂Co₂O₇
• 分子量: 398.22
• InChiKey: LUOZUDKADMDKFD-ZCIJAHFASA-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：

  四氟硼酸-二乙醚络合物 、 (μ-η²-4,4-dimethylpent-1-yn-3-ol)dicobalt hexacarbonyl 以 正戊烷 为溶剂， 反应 0.42h， 生成
  参考文献：
  名称：

  获取和利用丙炔基自由基的持久性：新型范式

  摘要：

  Three complementary methods for altering an intrinsic nature of propargyl radicals, from transient to persistent, were developed by fine-tuning the bulkiness and degree of substitution around the secondary and tertiary propargylic carbons, as well as by sterically enhancing a pi-bonded Co-2(CO)(6) metal core. The latter was employed, as a mechanistic tool, for precluding an acetylene allene rearrangement, stabilizing propargyl cations, and creating a steric hindrance that could provide for said transition from transient to persistent propargyl radicals. A window of opportunities was identified wherein the steric bulkiness in propargyl radicals remains below the "persistency threshold", providing good to excellent stereoselectivities in radical dimerization reactions (d,l 62-100%). Along with the persistency threshold for tertiary propargyl radicals (278.2 angstrom(3)), two different thresholds for persistency in secondary propargyl radicals were established-306.5 and 576.0 angstrom(3)-dependent upon the molecular architecture and the nature of the substituents populating the radical centers. Three alternative molecular platforms were designed to exploit a newly acquired dichotomy in allylic radicals (alpha-persistent-gamma-transient) and trichotomy in pentadienyl radicals (alpha-persistent-gamma-transient-epsilon- transient), providing access to molecular assemblies with contiguous 4 degrees-4 degrees, 4 degrees-3 degrees, and 3 degrees-3 degrees carbon atoms.

  DOI：

  10.1021/acs.organomet.6b00435
• 作为产物：
  描述：

  特戊醛 以 四氢呋喃 、 乙醚 为溶剂， 反应 3.5h， 生成 (μ-η²-4,4-dimethylpent-1-yn-3-ol)dicobalt hexacarbonyl
  参考文献：
  名称：

  获取和利用丙炔基自由基的持久性：新型范式

  摘要：

  Three complementary methods for altering an intrinsic nature of propargyl radicals, from transient to persistent, were developed by fine-tuning the bulkiness and degree of substitution around the secondary and tertiary propargylic carbons, as well as by sterically enhancing a pi-bonded Co-2(CO)(6) metal core. The latter was employed, as a mechanistic tool, for precluding an acetylene allene rearrangement, stabilizing propargyl cations, and creating a steric hindrance that could provide for said transition from transient to persistent propargyl radicals. A window of opportunities was identified wherein the steric bulkiness in propargyl radicals remains below the "persistency threshold", providing good to excellent stereoselectivities in radical dimerization reactions (d,l 62-100%). Along with the persistency threshold for tertiary propargyl radicals (278.2 angstrom(3)), two different thresholds for persistency in secondary propargyl radicals were established-306.5 and 576.0 angstrom(3)-dependent upon the molecular architecture and the nature of the substituents populating the radical centers. Three alternative molecular platforms were designed to exploit a newly acquired dichotomy in allylic radicals (alpha-persistent-gamma-transient) and trichotomy in pentadienyl radicals (alpha-persistent-gamma-transient-epsilon- transient), providing access to molecular assemblies with contiguous 4 degrees-4 degrees, 4 degrees-3 degrees, and 3 degrees-3 degrees carbon atoms.

  DOI：

  10.1021/acs.organomet.6b00435

文献信息

• Dynamic behavior of dicobalt hexacarbonyl propargyl cations and their reactions with chiral nucleophiles
  作者：Stuart L. Schreiber、Michael T. Klimas、Tarek Sammakia

  DOI：10.1021/ja00253a030

  日期：1987.9

  4-Phenyl-2,4,6-triazatetra~yclo[6.3.2.0~~~.0~~~] trideca- 10,12-diene-3,5dione was prepared by the reported procedure.’ Spectral parameters are as follows: I3C NMR (CDCI,, 30 “C, 25.2 MHz, CHC1, assigned as 76.91 ppm) 6 73.750 (Cl/C5), 40.957 (C2/C4/C6/C8), 127.532 (C6/C9), 131.516, 127.752 (ipso/para C), 128.830, 125.435 (meta/para C), 148.573 (C=O); ’H NMR (CDzCIz, XL 200 MHz, 30 OC, tetramethylsilane)

  4-Phenyl-2,4,6-triazatetra-yclo[6.3.2.0~~~.0~~~] trideca-10,12-diene-3,5dione 通过报道的程序制备。光谱参数如下： I3C NMR (CDCI,, 30"C, 25.2 MHz, CHC1, 指定为 76.91 ppm) 6 73.750 (Cl/C5), 40.957 (C2/C4/C6/C8), 127.592 (C6/C8) ), 131.516, 127.752 (ipso/para C), 128.830, 125.435 (meta/para C), 148.573 (C=O); 'H NMR (CDzClz, XL 200 MHz, 30 OC, 四甲基硅烷) 6 7.49 (Ph), 4.92 (t, J = 7.7 Hz, Hl/H5), 4.35 (主要偶联 t, J = 7.7 Hz, H2/H4/