(4S,14S)-(-)-4,14-dibenzyl-6,9,12-trioxa-3,15,21-triazabicyclo<15.3.1>heneicosa-1(21),17,19-triene-2,16-dione | 143331-25-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: (4S,14S)-(-)-4,14-dibenzyl-6,9,12-trioxa-3,15,21-triazabicyclo<15.3.1>heneicosa-1(21),17,19-triene-2,16-dione
• 英文别名: (4S,14S)-4,14-dibenzyl-6,9,12-trioxa-3,15,21-triazabicyclo[15.3.1]henicosa-1(21),17,19-triene-2,16-dione
• CAS: 143331-25-3
• 化学式: C₂₉H₃₃N₃O₅
• 分子量: 503.598
• InChiKey: MDTNUQIGEIGFON-DQEYMECFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  98.8
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4S,14S)-(-)-4,14-dibenzyl-6,9,12-trioxa-3,15,21-triazabicyclo<15.3.1>heneicosa-1(21),17,19-triene-2,16-dione 在 劳森试剂 、 镍 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 21.0h， 生成 (4S,14S)-(+)-4,14-dibenzyl-6,9,12-trioxa-3,15,21-triazabicyclo<15.3.1>heneicosa-1(21),17,19-triene
  参考文献：
  名称：

  New symmetrical chiral dibenzyl- and diphenyl-substituted diamido-, dithionoamido-, diaza-, and azapyridino-18-crown-6 ligands

  摘要：

  Eleven new chiral macrocycles (1-11, see Figure 1) of the pyridino-18-crown-6 type have been prepared. Nine diazapyridin-crown ligands contain two amide (1, R = benzyl; 4, R = phenyl), two N-methylamide (7, R = phenyl), two thionoamide (2, R = benzyl; 5, R = phenyl), two N-methylthionoamide (8, R = phenyl), two amine (3, R = benzyl; 6, R = phenyl), or two N-methylamine (9, R = phenyl) groups incorporated into the macroring. The appropriate chiral diamine was treated with dimethyl 2,6-pyridinedicarboxylate (or 2,6-pyridinedicarbonyl dichloride), O,O '-dimethyl 2,6-pyridinedicarbothioate, or 2,6-pyridinedimethyl ditosylate to prepare these materials. The macrocyclic diamides were also converted to the macrocyclic dithionoamides using Lawesson's reagent and the latter macrocycles were reduced to the diamines. A new symmetrically substituted dimethylazapyridino-18-crown-6 ligand (10) and its N-acetyl derivative 11 were also prepared. The interactions of some of the new chiral ligands with (R)- and (S)-[alpha-(l-naphthyl)ethyl]ammonium perchlorate were studied by H-1 NMR spectral techniques. The degree of enantiomeric recognition was determined by the difference of the free energy of activation values (DELTADELTAG double dagger) and the difference in log K values for these interactions. The X-ray analyses of the dithionoamido ligands (2, 5, and 8) showed severe deviations of the S and N atoms from the plane of the pyridine ring, especially in the case of 8. The optical rotation of 8 changed with time due to conformational changes. The relevant conformations of 8 are discussed in light of the X-ray crystallography, molecular mechanics, and H-1 NMR spectra.

  DOI：

  10.1021/jo00046a020
• 作为产物：
  描述：

  吡啶-2.6-二羧酸二甲酯 、 (2S)-1-[2-[2-[(2S)-2-amino-3-phenylpropoxy]ethoxy]ethoxy]-3-phenylpropan-2-amine 在 对甲苯磺酸钠 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 144.0h， 以29%的产率得到(4S,14S)-(-)-4,14-dibenzyl-6,9,12-trioxa-3,15,21-triazabicyclo<15.3.1>heneicosa-1(21),17,19-triene-2,16-dione
  参考文献：
  名称：

  New symmetrical chiral dibenzyl- and diphenyl-substituted diamido-, dithionoamido-, diaza-, and azapyridino-18-crown-6 ligands

  摘要：

  Eleven new chiral macrocycles (1-11, see Figure 1) of the pyridino-18-crown-6 type have been prepared. Nine diazapyridin-crown ligands contain two amide (1, R = benzyl; 4, R = phenyl), two N-methylamide (7, R = phenyl), two thionoamide (2, R = benzyl; 5, R = phenyl), two N-methylthionoamide (8, R = phenyl), two amine (3, R = benzyl; 6, R = phenyl), or two N-methylamine (9, R = phenyl) groups incorporated into the macroring. The appropriate chiral diamine was treated with dimethyl 2,6-pyridinedicarboxylate (or 2,6-pyridinedicarbonyl dichloride), O,O '-dimethyl 2,6-pyridinedicarbothioate, or 2,6-pyridinedimethyl ditosylate to prepare these materials. The macrocyclic diamides were also converted to the macrocyclic dithionoamides using Lawesson's reagent and the latter macrocycles were reduced to the diamines. A new symmetrically substituted dimethylazapyridino-18-crown-6 ligand (10) and its N-acetyl derivative 11 were also prepared. The interactions of some of the new chiral ligands with (R)- and (S)-[alpha-(l-naphthyl)ethyl]ammonium perchlorate were studied by H-1 NMR spectral techniques. The degree of enantiomeric recognition was determined by the difference of the free energy of activation values (DELTADELTAG double dagger) and the difference in log K values for these interactions. The X-ray analyses of the dithionoamido ligands (2, 5, and 8) showed severe deviations of the S and N atoms from the plane of the pyridine ring, especially in the case of 8. The optical rotation of 8 changed with time due to conformational changes. The relevant conformations of 8 are discussed in light of the X-ray crystallography, molecular mechanics, and H-1 NMR spectra.

  DOI：

  10.1021/jo00046a020

文献信息

• New symmetrical chiral dibenzyl- and diphenyl-substituted diamido-, dithionoamido-, diaza-, and azapyridino-18-crown-6 ligands
  作者：Peter Huszthy、Masatoshi Oue、Jerald S. Bradshaw、Cheng Y. Zhu、Tingmin Wang、N. Kent Dalley、Janet C. Curtis、Reed M. Izatt

  DOI：10.1021/jo00046a020

  日期：1992.9

  Eleven new chiral macrocycles (1-11, see Figure 1) of the pyridino-18-crown-6 type have been prepared. Nine diazapyridin-crown ligands contain two amide (1, R = benzyl; 4, R = phenyl), two N-methylamide (7, R = phenyl), two thionoamide (2, R = benzyl; 5, R = phenyl), two N-methylthionoamide (8, R = phenyl), two amine (3, R = benzyl; 6, R = phenyl), or two N-methylamine (9, R = phenyl) groups incorporated into the macroring. The appropriate chiral diamine was treated with dimethyl 2,6-pyridinedicarboxylate (or 2,6-pyridinedicarbonyl dichloride), O,O '-dimethyl 2,6-pyridinedicarbothioate, or 2,6-pyridinedimethyl ditosylate to prepare these materials. The macrocyclic diamides were also converted to the macrocyclic dithionoamides using Lawesson's reagent and the latter macrocycles were reduced to the diamines. A new symmetrically substituted dimethylazapyridino-18-crown-6 ligand (10) and its N-acetyl derivative 11 were also prepared. The interactions of some of the new chiral ligands with (R)- and (S)-[alpha-(l-naphthyl)ethyl]ammonium perchlorate were studied by H-1 NMR spectral techniques. The degree of enantiomeric recognition was determined by the difference of the free energy of activation values (DELTADELTAG double dagger) and the difference in log K values for these interactions. The X-ray analyses of the dithionoamido ligands (2, 5, and 8) showed severe deviations of the S and N atoms from the plane of the pyridine ring, especially in the case of 8. The optical rotation of 8 changed with time due to conformational changes. The relevant conformations of 8 are discussed in light of the X-ray crystallography, molecular mechanics, and H-1 NMR spectra.