3-methoxy-1-butyne-dicobalt hexacarbonyl | 102286-06-6

• 英文名称: 3-methoxy-1-butyne-dicobalt hexacarbonyl
• CAS: 102286-06-6
• 化学式: C₁₁H₈Co₂O₇
• 分子量: 370.167
• InChiKey: PUBQASPBZLCHHD-CFYCIBGSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  3-methoxy-1-butyne-dicobalt hexacarbonyl 、 在 二氯乙基铝 作用下， 以 二氯甲烷 为溶剂， 生成 syn-Co₂(CO)6(HCCHCH₃CHCH₃COPh) 、 anti-Co₂(CO)6(HCCHCH₃CHCH₃COPh)
  参考文献：
  名称：

  A Lewis acid-mediated version of the Nicholas reaction: Synthesis of syn-alkylated products and cobalt-complexed cycloalkynes

  摘要：

  DOI：

  10.1021/ja00271a066

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/
• Acquiring a Prognostic Power in Co₂(CO)₆-Mediated, Cobaltocene-Induced Radical Dimerizations of Propargyl Triflates
  作者：Gagik G. Melikyan、Ryan Davis、Bryan Anker、Deborah Meron、Kellyanne Duncan

  DOI：10.1021/acs.organomet.6b00730

  日期：2016.12.27

  Cobalt-complexed propargyl triflates can be generated in situ from methyl propargyl ethers and triflic anhydride and then reduced with cobaltocene to topologically and functionally diverse 1,5-alkadiynes. The electronic effect of an alpha-substituent is shown to attenuate the ionic nature of an alpha-C-OTf bond and thus its reducibility with cobaltocene. The powerful pi-donors, such as phenyl, naphthyl, alkenyl, alkynyl, and alkoxy groups, provide the ionicity of alpha-C-OTf bonds and make them suitable recipients for a single-electron delivery from cobaltocene. sigma-Donors (alkyl groups), a H atom, and sigma/pi-acceptors (ester groups) do not sufficiently stabilize propargyl cations, maintaining the covalent nature of alpha-C-OTf bonds and making them resistant toward the reducing agent. A newly acquired ability to differentiate between the alpha-C-OTf bonds is used in polyethers for the regioselective reduction and radical dimerization in select propargylic positions, thus paving the way for a long sought after radical-ionic alpha,alpha'-functionalization in propargyl systems. Heterolytic bond dissociation energy (BDE) values are used to quantitate the impact of alpha substituents, to identify the "ionic" and "covalent" domains for electronically diverse propargyl triflates (ionic: BDEhet 238-271 kcal/mol; covalent: BDEhet 277-315 kcal/mol), and also to make predictions for new types of substituents and new classes of organic compounds.