6,6-Dibutyl-1,11-dimethoxy-2,4,8,10-tetrakis(3,4,5-trifluorophenyl)-5,7-dihydrobenzo[d][2]benzazepin-6-ium;bromide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: 6,6-Dibutyl-1,11-dimethoxy-2,4,8,10-tetrakis(3,4,5-trifluorophenyl)-5,7-dihydrobenzo[d][2]benzazepin-6-ium;bromide
• 英文别名: 6,6-dibutyl-1,11-dimethoxy-2,4,8,10-tetrakis(3,4,5-trifluorophenyl)-5,7-dihydrobenzo[d][2]benzazepin-6-ium;bromide
• 化学式: Br*C₄₈H₃₈F₁₂NO₂
• 分子量: 968.72
• InChiKey: SNTALQJBFOZBCQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.14
• 重原子数：
  64
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为产物：
  描述：

  3,4,5-三氟苯硼酸 在 N-溴代丁二酰亚胺(NBS) 、 tripotassium phosphate "n" hydrate 、 偶氮二异丁腈 、 palladium diacetate 、 potassium carbonate 、 三(邻甲基苯基)磷 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 、 苯 为溶剂， 反应 30.5h， 生成 6,6-Dibutyl-1,11-dimethoxy-2,4,8,10-tetrakis(3,4,5-trifluorophenyl)-5,7-dihydrobenzo[d][2]benzazepin-6-ium;bromide
  参考文献：
  名称：

  Design of Chiral Phase Transfer Catalyst with Conformationally Fixed Biphenyl Core:  Application to Asymmetric Alkylation of Glycine Derivatives

  摘要：

  Chiral phase transfer catalysts (S)-1a and (S)-1b with a conformationally fixed biphenyl core were conveniently prepared from the known (S)- 6,6')-dimethylbiphenyl- 2,2')- diol 2 in five steps. These catalysts, (S)-1a and ( S)-1b, are readily applicable to asymmetric alkylation of glycine derivatives with excellent enantioselectivity. In particular, catalyst (S)-1b was found to exhibit a unique temperature effect on the enantioselectivity, and asymmetric alkylation of glycine derivatives at room temperature gave a higher ee than that at 0 degrees C.

  DOI：

  10.1021/op0602324
• 作为试剂：
  描述：

  N-二苯亚甲基-甘氨酸叔丁酯 、 碘乙烷 在 6,6-Dibutyl-1,11-dimethoxy-2,4,8,10-tetrakis(3,4,5-trifluorophenyl)-5,7-dihydrobenzo[d][2]benzazepin-6-ium;bromide 、 potassium hydroxide 作用下， 以 水 、 甲苯 为溶剂， 反应 10.0h， 以86%的产率得到(R)-tert-butyl 2-[(diphenylmethylene)amino]butanoate
  参考文献：
  名称：

  Design of Chiral Phase Transfer Catalyst with Conformationally Fixed Biphenyl Core:  Application to Asymmetric Alkylation of Glycine Derivatives

  摘要：

  Chiral phase transfer catalysts (S)-1a and (S)-1b with a conformationally fixed biphenyl core were conveniently prepared from the known (S)- 6,6')-dimethylbiphenyl- 2,2')- diol 2 in five steps. These catalysts, (S)-1a and ( S)-1b, are readily applicable to asymmetric alkylation of glycine derivatives with excellent enantioselectivity. In particular, catalyst (S)-1b was found to exhibit a unique temperature effect on the enantioselectivity, and asymmetric alkylation of glycine derivatives at room temperature gave a higher ee than that at 0 degrees C.

  DOI：

  10.1021/op0602324

文献信息

• Convenient preparation of chiral phase-transfer catalysts with conformationally fixed biphenyl core for catalytic asymmetric synthesis of α-alkyl- and α,α-dialkyl-α-amino acids: application to the short asymmetric synthesis of BIRT-377
  作者：Yong-Gang Wang、Mitsuhiro Ueda、Xisheng Wang、Zhenfu Han、Keiji Maruoka

  DOI：10.1016/j.tet.2007.02.079

  日期：2007.6

  Chiral phase-transfer catalysts (S)-1a, (S)-1b, and (S)-2 with conformationally fixed biphenyl cores were conveniently prepared from the known, easily available (S)-6,6′-dimethylbiphenyl-2,2′-diol 3 and (S)-4,5,6,4′,5′,6′-hexamethoxybiphenyl-2,2′-dicarboxylic acid 14, respectively, in five steps. The catalysts, (S)-1a and (S)-1b are readily applicable to asymmetric alkylation of N-(diphenylmethylene)glycine

  具有构象固定的联苯核的手性相转移催化剂（S）-1a，（S）-1b和（S）-2由已知的，易于获得的（S）-6,6'-二甲基联苯-2， 2'-二醇3和（S）-4,5,6,4'，5'，6'-六甲氧基联苯-2,2'-二羧酸14分别在五个步骤中。催化剂（S）-1a和（S）-1b易于用于N-（二苯基亚甲基）甘氨酸叔丁基的不对称烷基化丁酯具有出色的对映选择性。特别地，发现催化剂（S）-1b对对映选择性表现出独特的温度影响，并且甘氨酸衍生物在室温下的不对称烷基化比在0℃下具有更高的对映体过量。此外，催化剂（S）-2在N-（二苯基亚甲基）甘氨酸叔丁酯和N-（对氯苯基亚甲基）丙氨酸叔丁酯的不对称烷基化反应中表现出较高的催化性能（0.01-1 mol％）。丁酯与现有的手性相转移催化剂相比，从而可以实现通用且有用的程序，用于高度实用的对映选择性合成结构多样的天然和非天然α-烷基-α-氨基酸以及α，α-二烷基- α
• OPTICALLY ACTIVE QUATERNARY AMMONIUM SALT HAVING AXIAL ASYMMETRY, AND METHOD FOR PRODUCING ALPHA-AMINO ACID AND DERIVATIVE THEREOF BY USING THE SAME
  申请人：Maruoka Keiji

  公开号：US20100029935A1

  公开（公告）日：2010-02-04

  The present invention discloses an optically active quarternary ammonium salt having axial asymmetry and a method for producing an α-amino acid and a derivative thereof using the same. The optically active quarternary ammonium salt having axial asymmetry of the present invention is a chiral phase-transfer catalyst that has a simple structure and that can be produced in a smaller number of process steps. The compound of the present invention is very useful as a phase-transfer catalyst in the synthesis of an α-alkyl-α-amino acid and a derivative thereof as well as an α,α-dialkyl-α-amino acid and a derivative thereof. Therefore, the compound of the present invention can be used in the development of novel foods and pharmaceuticals.

  本发明公开了一种具有轴向不对称性的光学活性季铵盐，以及利用该季铵盐制备α-氨基酸及其衍生物的方法。本发明的具有轴向不对称性的光学活性季铵盐是一种手性相转移催化剂，具有简单的结构，并且可以在较少的工艺步骤中生产。本发明的化合物在合成α-烷基-α-氨基酸及其衍生物以及α,α-二烷基-α-氨基酸及其衍生物时非常有用作为相转移催化剂。因此，本发明的化合物可用于开发新型食品和药物。