(4R,5R)-2-o-Tolyl-[1,3]dioxolane-4,5-dicarboxylic acid bis-dimethylamide | 141376-07-0

• 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: (4R,5R)-2-o-Tolyl-[1,3]dioxolane-4,5-dicarboxylic acid bis-dimethylamide
• CAS: 141376-07-0
• 化学式: C₁₆H₂₂N₂O₄
• 分子量: 306.362
• InChiKey: UKCWDEYZSXNLBS-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.95
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  59.08
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (4R,5R)-2-o-Tolyl-[1,3]dioxolane-4,5-dicarboxylic acid bis-dimethylamide 在 lithium aluminium tetrahydride 作用下， 生成 ((4S,5S)-5-Dimethylaminomethyl-2-o-tolyl-[1,3]dioxolan-4-ylmethyl)-dimethyl-amine
  参考文献：
  名称：

  Asymmetric deprotonation and complexation reactions mediated by chiral ketals as a route to ortho-disubstituted (.eta.6-arene)Cr(CO)3 complexes

  摘要：

  A series of chiral ketals derived from an aryl ketone or aldehyde and one of several C2-symmetrical diols were converted to their corresponding (eta-6-arene)Cr(CO)s complexes. The resultant 1,3-dioxolanes were trans substituted at C-4 and C-5 by groups CH2X, where X = H (1), OCH3 (2), or N(CH3)2 (3). Ortho deprotonation was attempted on complexes 1-3 using tert-butyllithium in THF solution to afford the corresponding lithio derivatives, which were treated with a variety of electrophiles (MeOSO2F, TMSCl, Ph2C(O), Ph2PCl). Although 1 gave a complex mixture of products, complexes 2 and 3 afforded good yields of disubstituted complexes (with the exception that the lithiated derivative of 3 did not undergo methylation when treated with MeOSO2F). The stereoselectivity of the reactions was determined by NMR spectroscopy and found to be in the range of 3:1 for 2 and >9.1 for 3. The sense of diastereoselection were identified by chemical correlations (for compounds derived from 2) and by circular dichroism spectroscopy. Poor diastereoselection was obtained when this protocol was performed on the corresponding acetal ultimately derived from benzaldehyde and N,N,N',N-tetramethyl-1,4-diamino-2,3-butanediol. In addition, a related series of ortho-disubstituted arenes bearing chiral ketal or acetal substituents in the benzylic position were subjected to complexation reactions with (naphthalene)Cr(CO)3 in dibutyl ether. The best diastereoselectivity observed with this methodology was 48%, obtained with the acetal derived from o-tolualdehyde and N,N,N',N-tetramethyltartramide.

  DOI：

  10.1021/jo00039a012
• 作为产物：
  描述：

  N,N,N’,N’-四甲基-L-酒石酰胺 、 1-(二甲氧基甲基)-2-甲基苯 在 对甲苯磺酸 作用下， 生成 (4R,5R)-2-o-Tolyl-[1,3]dioxolane-4,5-dicarboxylic acid bis-dimethylamide
  参考文献：
  名称：

  Asymmetric deprotonation and complexation reactions mediated by chiral ketals as a route to ortho-disubstituted (.eta.6-arene)Cr(CO)3 complexes

  摘要：

  A series of chiral ketals derived from an aryl ketone or aldehyde and one of several C2-symmetrical diols were converted to their corresponding (eta-6-arene)Cr(CO)s complexes. The resultant 1,3-dioxolanes were trans substituted at C-4 and C-5 by groups CH2X, where X = H (1), OCH3 (2), or N(CH3)2 (3). Ortho deprotonation was attempted on complexes 1-3 using tert-butyllithium in THF solution to afford the corresponding lithio derivatives, which were treated with a variety of electrophiles (MeOSO2F, TMSCl, Ph2C(O), Ph2PCl). Although 1 gave a complex mixture of products, complexes 2 and 3 afforded good yields of disubstituted complexes (with the exception that the lithiated derivative of 3 did not undergo methylation when treated with MeOSO2F). The stereoselectivity of the reactions was determined by NMR spectroscopy and found to be in the range of 3:1 for 2 and >9.1 for 3. The sense of diastereoselection were identified by chemical correlations (for compounds derived from 2) and by circular dichroism spectroscopy. Poor diastereoselection was obtained when this protocol was performed on the corresponding acetal ultimately derived from benzaldehyde and N,N,N',N-tetramethyl-1,4-diamino-2,3-butanediol. In addition, a related series of ortho-disubstituted arenes bearing chiral ketal or acetal substituents in the benzylic position were subjected to complexation reactions with (naphthalene)Cr(CO)3 in dibutyl ether. The best diastereoselectivity observed with this methodology was 48%, obtained with the acetal derived from o-tolualdehyde and N,N,N',N-tetramethyltartramide.

  DOI：

  10.1021/jo00039a012