S,S-diacetyl-3,3-bis<<4'-<(dimethylamino)methyl>benzyl>thio>-1,5-pentanediol | 161487-80-5

• 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: S,S-diacetyl-3,3-bis<<4'-<(dimethylamino)methyl>benzyl>thio>-1,5-pentanediol
• CAS: 161487-80-5
• 化学式: C₂₉H₄₂N₂O₂S₄
• 分子量: 578.929
• InChiKey: SCLSVLHZVXUHDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.01
• 重原子数：
  37.0
• 可旋转键数：
  16.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  40.62
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  S,S-diacetyl-3,3-bis<<4'-<(dimethylamino)methyl>benzyl>thio>-1,5-pentanediol 在 氨 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.0h， 生成 17,17-dimethyl-19H-m-dioxino<19,1-c>-6,6-bis<<4'-<(dimethylamino)methyl>benzyl>thio>-3,9-dithia-12-azabicyclo<9.2.2>pentadeca-11,13,14-triene
  参考文献：
  名称：

  Geometric Control of a Pyridoxal-Catalyzed Aldol Condensation

  摘要：

  A chiral cyclophane derivative of pyridoxal has been synthesized that has amino groups oriented specifically over one face of the cofactor. The compound catalyzes the formation of threonine and allo-threonine from glycine and acetaldehyde with enantioinductions that are a function of pH, reversing the optical selectivity between low pH and high pH. The stereochemical results are compared with those of structurally related pyridoxal cyclophanes that lack titratable catalytic groups. Explanations are advanced for this stereochemical reversal and for the otherwise surprising preference of most of these compounds to react on the more hindered face of the pyridoxal. Models indicate that the transamination intermediate is distorted by the transannular chain, and stereoelectronic arguments predict that this distortion should lead to reaction on the face that carries the chain, as observed. The stereochemical reversal with the attached (dimethylamino)alkyl group, as a function of pH, may reflect catalysis by the protonated form, but metal coordination by the basic form cannot be excluded.

  DOI：

  10.1021/ja00104a004
• 作为产物：
  描述：

  diethyl 3,3-bis<<4'-(dimethylcarbamoyl)benzyl>thio>glutarate 在 N,N-二异丙基乙胺 、 红铝 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基乙酰胺 、 甲苯 为溶剂， 反应 39.0h， 生成 S,S-diacetyl-3,3-bis<<4'-<(dimethylamino)methyl>benzyl>thio>-1,5-pentanediol
  参考文献：
  名称：

  Geometric Control of a Pyridoxal-Catalyzed Aldol Condensation

  摘要：

  A chiral cyclophane derivative of pyridoxal has been synthesized that has amino groups oriented specifically over one face of the cofactor. The compound catalyzes the formation of threonine and allo-threonine from glycine and acetaldehyde with enantioinductions that are a function of pH, reversing the optical selectivity between low pH and high pH. The stereochemical results are compared with those of structurally related pyridoxal cyclophanes that lack titratable catalytic groups. Explanations are advanced for this stereochemical reversal and for the otherwise surprising preference of most of these compounds to react on the more hindered face of the pyridoxal. Models indicate that the transamination intermediate is distorted by the transannular chain, and stereoelectronic arguments predict that this distortion should lead to reaction on the face that carries the chain, as observed. The stereochemical reversal with the attached (dimethylamino)alkyl group, as a function of pH, may reflect catalysis by the protonated form, but metal coordination by the basic form cannot be excluded.

  DOI：

  10.1021/ja00104a004