CpW(CO)3(η(1)-4-methyl-5-isopropyl-2-furyl) | 156974-09-3

• 英文名称: CpW(CO)3(η(1)-4-methyl-5-isopropyl-2-furyl)
• CAS: 156974-09-3
• 化学式: C₁₆H₁₆O₄W
• 分子量: 456.151
• InChiKey: WKQFCUPKIZDZTH-UHFFFAOYSA-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：

  CpW(CO)3(η(1)-4-methyl-5-isopropyl-2-furyl) 在 CF₃SO₃H 作用下， 以 二氯甲烷-D2 为溶剂， 以65%的产率得到
  参考文献：
  名称：

  Wang, Shin-Hwan; Shiu, Lin-Hung; Shu, Hsin-Guo, Journal of the American Chemical Society, 1994, vol. 116, # 13, p. 5967 - 5968

  摘要：

  DOI：
• 作为产物：
  描述：

  CpW(CO)3(η(1)-4metyl-5-isopropyl-3-furyl) 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 以96%的产率得到CpW(CO)3(η(1)-4-methyl-5-isopropyl-2-furyl)
  参考文献：
  名称：

  Tungsten η¹-Five-Membered Oxygenated Heterocycles Derived from Tungsten η¹-Propargyl Compounds:  Systematic Syntheses, Structural Rearrangement, Electrophilic Alkylations, and Oxidative Demetalations

  摘要：

  In the presence of BF3 . Et(2)O, tungsten eta(1)-propargyl complexes reacted smoothly with aldehydes to give tungsten eta-2,5-dihydro-3-furyl complexes 1-3. Treatment of 1-3 with Ph(3)CBF(4) in CH2Cl2 (-60 degrees C, 1 h) delivered tungsten eta(1)-3-furylidene complexes 4-6 which underwent skeletal rearrangement to eta(1)-2-furylidene 13-15 isomers when warmed to 5 degrees C. Treatment of 4-6 with Et(3)N at -60 degrees C produced tungsten eta(1)-3-furyl complexes 7-9 which were isomerized to eta(1)-2-furyl isomers 10-12 by a strong Bronsted acid. Protonation of 10-12 by CF3CO2H yielded eta(1)-furylidene complexes 13-15. The two exceptional isomerizations were examined by in situ H-1 NMR studies. Further oxidation of eta(1)-2furyl compounds 10-12 with m-chloroperbenzoic acid gave tungsten eta(1)-Delta(3)-butenolides 16-18. Tungsten eta(1)-3-furyl complexes 7 and 9 underwent alkylation with trimethoxymethane and aldehydes at -60 degrees C to yield eta(1)-3-furylidene cationic precipitates that were subsequently reduced with NaBH3CN to yield complex eta(1)-2,5-dihydro-3-furyl compounds in good diastereoselectivity; the stereochemical courses were distinct for 7 and 9. Tungsten eta(1)-2,5-dihydro-3-furyl, eta(1)-2-furyl, eta(1)-3-furyl, and eta(1)-Delta(3)-butenolide complexes were decomplexed with appropriate reagents to liberate 2,5-dihydrofurans, furans, and Delta(3)- and Delta(2)-butenolides in reasonable yields.

  DOI：

  10.1021/ja9518888