(η(5)-C5H5)2ZrCl(OC(=CHCH3)NPh2) | 168477-43-8

• 英文名称: (η(5)-C5H5)2ZrCl(OC(=CHCH3)NPh2)
• CAS: 168477-43-8；168477-44-9
• 化学式: C₂₅H₂₄ClNOZr
• 分子量: 481.149
• InChiKey: WAXLHRKFCCBFGW-UHFFFAOYSA-L

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：

  (η(5)-C5H5)2ZrCl(OC(=CHCH3)NPh2) 、 对甲基苯乙酮 以 氘代苯 为溶剂， 生成 (η(5)-C5H5)2ZrCl(OC(Me)(p-MeC6H4)CH(Me)CONPh2)
  参考文献：
  名称：

  酰胺基烯醇酸酯的锆辅助羟醛缩合反应：N，N-二苯基乙酰胺和N，N-二苯基丙酰胺醇酸酯与苯甲醛和对位苯乙酮反应的结构和动力学分析

  摘要：

  The deprotonation of N,N-diphenyl amides with LDA and subsequent reaction with [(cp)(2)ZrCl2] (cp = eta(5)-C5H5) allowed the enolate complexes [{Ph(2)NC(CH2)O}Zr(cp)(2)(Cl)] (5) and [{Ph(2)NC(CHCH3)O}Zr(cp)(2)(Cl)] (6) to be isolated. The crystal structure of 6 is reported. Reaction of 5 with [Cr(CO)(5)]. THF gave [Ph(2)NC{CH2Cr(CO)(5)}{OZr(Cl)(cp)(2)}] (7), an 0- and C-bonded dimetallic amido enolate. Reaction of 5 and 6 with benzaldehyde gave the corresponding aldol products 8 and 9; according to previous reports, the conversion of 6 into 9 is syn selective. Reaction of 6 with acetophenone followed by addition of silver triflate gave the complex [Ph(2)NC(=O)CH(CH3)C(Me)(Ph)OZr(cp)(2)(Cl)(OSO2CF3)] (11) as a diastereoisomeric mixture in the ratio anti:syn = 65:35. The crystal structure of sym-11 is reported. This cyclic complex mimics the postulated cyclic transition state of the aldol reaction mediated by zirconium amide enolates. A kinetic investigation of the reaction of 6 with acetophenone was performed and gave the following activation parameters: Delta H-double dagger = 38.3 +/- 0.9 kJ mol(-1); Delta S-double dagger greater than or equal to -181 +/- 3 J mol(-1) K-1; Delta G(298)(double dagger) = 92.2 +/- 1.2 kJ mol(-1). A similar study with 4-fluoroacetophenone gave Delta H-double dagger = 43.5 +/- 1.3 kJ mol(-1), Delta S-double dagger greater than or equal to -167 +/- 4 J mol(-1) K-1, and Delta G(298)(double dagger) = 93.3 +/- 1.8 kJ mol(-1). The reaction rate at 320 K determined with 4-chloro-, 4-methyl-, and 4-nitroacetophenone allowed the determination of a Hammett plot with rho = 0.41. This value is implicit of a carbon-carbon bond-forming, rate-limiting step.

  DOI：

  10.1021/om00009a012
• 作为产物：
  描述：

  二氯二茂锆 、 N,N-diphenylpropionamide 在 LDA 作用下， 以 四氢呋喃 为溶剂， 以71%的产率得到(η(5)-C5H5)2ZrCl(OC(=CHCH3)NPh2)
  参考文献：
  名称：

  酰胺基烯醇酸酯的锆辅助羟醛缩合反应：N，N-二苯基乙酰胺和N，N-二苯基丙酰胺醇酸酯与苯甲醛和对位苯乙酮反应的结构和动力学分析

  摘要：

  The deprotonation of N,N-diphenyl amides with LDA and subsequent reaction with [(cp)(2)ZrCl2] (cp = eta(5)-C5H5) allowed the enolate complexes [{Ph(2)NC(CH2)O}Zr(cp)(2)(Cl)] (5) and [{Ph(2)NC(CHCH3)O}Zr(cp)(2)(Cl)] (6) to be isolated. The crystal structure of 6 is reported. Reaction of 5 with [Cr(CO)(5)]. THF gave [Ph(2)NC{CH2Cr(CO)(5)}{OZr(Cl)(cp)(2)}] (7), an 0- and C-bonded dimetallic amido enolate. Reaction of 5 and 6 with benzaldehyde gave the corresponding aldol products 8 and 9; according to previous reports, the conversion of 6 into 9 is syn selective. Reaction of 6 with acetophenone followed by addition of silver triflate gave the complex [Ph(2)NC(=O)CH(CH3)C(Me)(Ph)OZr(cp)(2)(Cl)(OSO2CF3)] (11) as a diastereoisomeric mixture in the ratio anti:syn = 65:35. The crystal structure of sym-11 is reported. This cyclic complex mimics the postulated cyclic transition state of the aldol reaction mediated by zirconium amide enolates. A kinetic investigation of the reaction of 6 with acetophenone was performed and gave the following activation parameters: Delta H-double dagger = 38.3 +/- 0.9 kJ mol(-1); Delta S-double dagger greater than or equal to -181 +/- 3 J mol(-1) K-1; Delta G(298)(double dagger) = 92.2 +/- 1.2 kJ mol(-1). A similar study with 4-fluoroacetophenone gave Delta H-double dagger = 43.5 +/- 1.3 kJ mol(-1), Delta S-double dagger greater than or equal to -167 +/- 4 J mol(-1) K-1, and Delta G(298)(double dagger) = 93.3 +/- 1.8 kJ mol(-1). The reaction rate at 320 K determined with 4-chloro-, 4-methyl-, and 4-nitroacetophenone allowed the determination of a Hammett plot with rho = 0.41. This value is implicit of a carbon-carbon bond-forming, rate-limiting step.

  DOI：

  10.1021/om00009a012