butane;tert-butyl-(N-ethyl-C-methylcarbonimidoyl)azanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;zirconium(4+);chloride | 583022-43-9

• 分子结构分类: 有机化合物 - 碳氢化合物
• 英文名称: butane;tert-butyl-(N-ethyl-C-methylcarbonimidoyl)azanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;zirconium(4+);chloride
• CAS: 583022-43-9；583029-41-8
• 化学式: C₂₂H₄₁ClN₂Zr
• 分子量: 460.258
• InChiKey: WWXYUTCZFWRGFP-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  13.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  异氰酸叔丁酯 、 butane;tert-butyl-(N-ethyl-C-methylcarbonimidoyl)azanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;zirconium(4+);chloride 以 正戊烷 为溶剂， 以100%的产率得到
  参考文献：
  名称：

  A Case for Asymmetric Hydrozirconation

  摘要：

  Hydrozirconation of cis-2-butene with Cp*ZrHCl[N(t-Bu)C(Me)N(Et)], generated in situ through hydrogenolysis of Cp*ZrCl(SiMe2Ph)[N(t-Bu)C(Me)N(Et)] (5), proceeds in high yield to produce a 1:2 mixture of the kinetically stable, diastereomeric sec-butyl complexes, 3a and 3b. Hydrozirconation of trans-2-butene under identical conditions provides a 2:1 mixture of 3a and 3b. Isolation of diastereomerically pure 3a was achieved through reaction of Cp*ZrCl2[N(t-Bu)C(Me)N(Et)] (4) with sec-butyllithium to provide a 2:1 ratio of 3a and 3b, followed by fractional crystallization. Crystallographic analysis of 3a establishes the relative configuration of the sec-butyl group with respect to the chiral zirconium center, thereby permitting construction of diastereomeric transition states that explain the origin of high face selectivity in the hydrozirconation of cis-2-butene. Finally, both iodinative zirconium-carbon bond cleavage and insertion of tert-butyl isocyanide into the zirconium-carbon bond of the sec-butyl group of 3a were found to proceed in high yield and with retention of the secondary alkyl structure. Together, these results provide a critical platform upon which efforts directed toward the asymmetric hydrozirconation of alkenes can be based.

  DOI：

  10.1021/ja0349453
• 作为产物：
  描述：

  反-2-丁烯 、 (η⁵-C5Me5)ZrCl(SiMe2Ph)[t-BuNC(Me)NEt] 、 氢气 以 正戊烷 为溶剂， 以35%的产率得到butane;tert-butyl-(N-ethyl-C-methylcarbonimidoyl)azanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;zirconium(4+);chloride
  参考文献：
  名称：

  A Case for Asymmetric Hydrozirconation

  摘要：

  Hydrozirconation of cis-2-butene with Cp*ZrHCl[N(t-Bu)C(Me)N(Et)], generated in situ through hydrogenolysis of Cp*ZrCl(SiMe2Ph)[N(t-Bu)C(Me)N(Et)] (5), proceeds in high yield to produce a 1:2 mixture of the kinetically stable, diastereomeric sec-butyl complexes, 3a and 3b. Hydrozirconation of trans-2-butene under identical conditions provides a 2:1 mixture of 3a and 3b. Isolation of diastereomerically pure 3a was achieved through reaction of Cp*ZrCl2[N(t-Bu)C(Me)N(Et)] (4) with sec-butyllithium to provide a 2:1 ratio of 3a and 3b, followed by fractional crystallization. Crystallographic analysis of 3a establishes the relative configuration of the sec-butyl group with respect to the chiral zirconium center, thereby permitting construction of diastereomeric transition states that explain the origin of high face selectivity in the hydrozirconation of cis-2-butene. Finally, both iodinative zirconium-carbon bond cleavage and insertion of tert-butyl isocyanide into the zirconium-carbon bond of the sec-butyl group of 3a were found to proceed in high yield and with retention of the secondary alkyl structure. Together, these results provide a critical platform upon which efforts directed toward the asymmetric hydrozirconation of alkenes can be based.

  DOI：

  10.1021/ja0349453