tungsten(carbonyl)3CH2CCMe | 32877-63-7

• 英文名称: tungsten(carbonyl)3CH2CCMe
• 英文别名: CpW(CO)3CH2C*CMe
• CAS: 32877-63-7
• 化学式: C₁₂H₁₀O₃W
• 分子量: 386.06
• InChiKey: IMLIRVIIPVYOAS-UHFFFAOYSA-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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tungsten(carbonyl)3CH2CCMe 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 以57%的产率得到CpW(CO)2COOCH(Me)CHCH2
  参考文献：
  名称：

  New Carbonylation Reaction of Tungsten−Propargyl Compounds via Protonation at a Prolonged Period

  摘要：

  The CpW(CO)(3)(eta(1)-CH2C equivalent to CR) (R = Me 1, Ph 2) complexes were treated with triflic acid (2.0 equiv) in cold dichloromethane (-78 degrees C), and after a long period to the mixture was added water or RNH2 to give good yields of carbonylation products CpW(CO)(2)(eta(1),eta(2)-CH2-CHCHR-Y-CO-) (R = Me, Ph; Y = RN, O). These products were fully characterized by appropriate physical methods including single-crystal X-ray diffraction. If a chiral amine such as (R)-methylbenzylamine was used in the reaction, two optically active isomers in equal proportions were obtained and further separated on a silica column. In the case of (C5Me5)W(CO)(3)(eta(1)-CH2C equivalent to CPh) (9), its reactions with triflic acid and water in the same reaction sequence produce (C5Me5)W(CO)(2)(eta(1),eta(2)-CH2CHCHPh-O-CO-) as two diastereomers which undergo mutual exchange according to variable-temperature H-1 NMR spectroscopy.

  DOI：

  10.1021/om980787q

文献信息

• Wido, Thomas M.; Young, George H.; Wojcicki, Andrew, Organometallics, 1988, vol. 7, # 2, p. 452 - 458
  作者：Wido, Thomas M.、Young, George H.、Wojcicki, Andrew、Calligaris, Mario、Nardin, Giorgio

  DOI：——

  日期：——
• Tungsten η¹-Five-Membered Oxygenated Heterocycles Derived from Tungsten η¹-Propargyl Compounds:  Systematic Syntheses, Structural Rearrangement, Electrophilic Alkylations, and Oxidative Demetalations
  作者：Hsin-Guo Shu、Lin-Hung Shiu、Shin-Hwan Wang、Sue-Lein Wang、Gene-Hsian Lee、Shie-Ming Peng、Rai-Shung Liu

  DOI：10.1021/ja9518888

  日期：1996.1.1

  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.
• Synthesis of heteronuclear metal-allenyl clusters: transition metal propargyl compounds as templates for the construction of mixed metal-metal bonds
  作者：George H. Young、Andrew Wojcicki、Mario Calligaris、Giorgio Nardin、Nevina Bresciani-Pahor

  DOI：10.1021/ja00199a087

  日期：1989.8
• Young, George H.; Raphael, Marline V.; Wojcicki, Andrew, Organometallics, 1991, vol. 10, # 6, p. 1934 - 1945
  作者：Young, George H.、Raphael, Marline V.、Wojcicki, Andrew、Calligaris, Mario、Nardin, Giorgio、Bresciani-Pahor, Nevina

  DOI：——

  日期：——
• Reactions of tungsten and molybdenum propargyl complexes with Co2(CO)8, Co4(CO)12, and Cp2Mo2(CO)4. A crossover study of formation of (CO)3Cp(CO)2
  作者：George H. Young、Andrew Wojcicki

  DOI：10.1016/0022-328x(90)85103-6

  日期：1990.7