(4S,14S)-4,14-Diphenyl-3,15-bis-(toluene-4-sulfonyl)-6,9,12-trioxa-3,15,21-triaza-bicyclo[15.3.1]henicosa-1(20),17(21),18-triene | 143331-39-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4S,14S)-4,14-Diphenyl-3,15-bis-(toluene-4-sulfonyl)-6,9,12-trioxa-3,15,21-triaza-bicyclo[15.3.1]henicosa-1(20),17(21),18-triene
• 英文别名: (4S,14S)-3,15-bis-(4-methylphenyl)sulfonyl-4,14-diphenyl-6,9,12-trioxa-3,15,21-triazabicyclo[15.3.1]henicosa-1(21),17,19-triene
• CAS: 143331-39-9
• 化学式: C₄₁H₄₅N₃O₇S₂
• 分子量: 755.956
• InChiKey: GFLNWZNSBVHACQ-GYOJGHLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  53
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  132
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (4S,14S)-4,14-Diphenyl-3,15-bis-(toluene-4-sulfonyl)-6,9,12-trioxa-3,15,21-triaza-bicyclo[15.3.1]henicosa-1(20),17(21),18-triene 在 disodium hydrogenphosphate 、 sodium amalgam 作用下， 以 甲醇 为溶剂， 以37%的产率得到(4S,14S)-(+)-4,14-diphenyl-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：

  (1S,11S)-(+)-1,11-diamino-1,11-diphenyl-3,6,9-trioxaundecane 在 吡啶 、 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 73.0h， 生成 (4S,14S)-4,14-Diphenyl-3,15-bis-(toluene-4-sulfonyl)-6,9,12-trioxa-3,15,21-triaza-bicyclo[15.3.1]henicosa-1(20),17(21),18-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

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.