| 144810-86-6

• CAS: 144810-86-6
• 化学式: C₃₀H₃₂Cl₂P₂W
• 分子量: 709.288
• InChiKey: DTUOKUAMGOWBIR-UHFFFAOYSA-L

计算性质

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

反应信息

• 作为产物：
  描述：

  1,3-丁二烯 、 W^IICl2(PMePh2)4 以 甲苯 为溶剂， 以81%的产率得到
  参考文献：
  名称：

  Deoxygenative coupling of ketones and alkenes by tungsten(II) compounds

  摘要：

  Tungsten(II) compounds such as WCl2(PMePh2)4 (1) react with acetone and ethylene tro give a good yield of the tungsten(IV)-oxo complexes W(O)(CH2=CH2)Cl2(PMePh2)2 (4) and a moderate amount of 3-methyl-1-butene. Cyclopentanone and ethylene plus 1 yield 4 and vinylcyclopentane; methyl vinyl ketone and ethylene give 4 and 3-methyl- 1,4-pentadiene. The react ion of cyclopentanone and propylene with 1 yields a small amount of 2-cyclopentylpropene. Intramolecular deoxygenative coupling occurs with 6- and 7-en-2-ones to form 1-methyl-2-methylene-substituted cyclopentyl and cyclohexyl ring systems, respectively. The net result of these reactions is transfer of the ketone oxygen atom to tungsten, accompanied with its replacement by a hydrogen and a vinyl group. The suggested mechanism for this deoxygenative coupling (Scheme I) is coordination of both the ketone and ethylene to tungsten, coupling to form a 2-oxametal-lacyclopentane, beta-hydrogen elimination to an allyloxy hydride species, C-0 bond cleavage to an oxo allyl hydride complex, and reductive elimination of alkene. Consistent with the suggestion of an oxametallacycle, hydrolysis of the reaction mixture of 1 and 6-hepten-2-one provides stereospecifically trans-1,2-di-methylcyclopentanol. The enones methyl vinyl ketone and 5-hexen-2-one react with 1 to form stable complexes in which the enone is bound in an eta4 fashion, similar to the proposed mixed alkene ketone intermediates in the coupling reactions. A related tungsten(II) butadiene complex, WCl2(CH2=CHCH=CH2)(PMePhl)2, has also been isolated.

  DOI：

  10.1021/om00060a010

文献信息

• Jang, Soonhee; Atagi, Lauren M.; Mayer, James M., Journal of the American Chemical Society, 1990, vol. 112, # 17, p. 6413 - 6414
  作者：Jang, Soonhee、Atagi, Lauren M.、Mayer, James M.

  DOI：——

  日期：——