| 583029-59-8

• CAS: 583029-59-8
• 化学式: C₂₆H₄₈ClN₃Zr
• 分子量: 529.364
• InChiKey: HSEWIJQKCVFEJS-UHFFFAOYSA-M

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：

  、 异氰酸叔丁酯 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