| 560086-09-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• CAS: 560086-09-1
• 化学式: C₄₆H₃₄N₆NiO₄
• 分子量: 793.504
• InChiKey: ORBAXUOUDNNWPN-UHFFFAOYSA-L

反应信息

• 作为产物：
  描述：

  nickel(II) acetate tetrahydrate 、 9,14-Dioxa-2,21,28,36,44,51-hexazadecacyclo[24.18.8.14,8.115,19.02,42.021,29.022,27.030,35.038,43.045,50]tetrapentaconta-1(44),4(54),5,7,15,17,19(53),22,24,26,28,30,32,34,38(43),39,41,45,47,49-icosaene-37,52-dione 以 甲醇 、 二氯甲烷 为溶剂， 以94%的产率得到
  参考文献：
  名称：

  Ruffling-Induced Chirality:  Synthesis, Metalation, and Optical Resolution of Highly Nonplanar, Cyclic, Benzimidazole-Based Ligands

  摘要：

  Expedient five-step syntheses of a cyclic bis(benzimidazole)-based amide 5 and two sterically more hindered analogues 23-24 have been developed. These amides are chiral due to the inherent ruffling of the macrocyclic plane. Racemization of the optical antipodes of these compounds has been studied using dynamic chiral stationary phase HIPLC. These studies reveal that, while the parent amide 5 racemizes rapidly, for the sterically more hindered amides 23-24, the rate of racemization is significantly reduced. Bis(benzimidazole)-based amides 5 and 23-24 form stable Ni(II) complexes 25-27, respectively. Like their parent ligands, complexes 25-27 are chiral due to their highly ruffled geometry. Studies of these complexes by chiral stationary phase HPLC reveal that metalation leads to a much lower rate of racemization. Incorporation of a strap can slow racemization even further. A series of strapped cyclic amides 54-57, along with their corresponding dinners 58-61, have been prepared. The rate of racernization for amides 54-57 is strongly dependent on the length of the strap. X-ray single-crystal structure analysis of the Ni(II) complex of strapped amide 54 reveals that the bis(benzimidazole) core retains its highly ruffled shape, with the two phenyl rings of the macrocycle located anti to the strap. Chiral separation of strapped ligands 54-57 and their corresponding Ni(II) complexes is shown to be facile by chiral stationary phase HPLC.

  DOI：

  10.1021/ja030196d