(5S)-5<(4S,6R)-2,2-dimethyl-6-methyl-1,3-dioxan-4-yl>-2-hexanone dimethylhydrazone | 131685-62-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5S)-5<(4S,6R)-2,2-dimethyl-6-methyl-1,3-dioxan-4-yl>-2-hexanone dimethylhydrazone
• CAS: 131685-62-6；131725-12-7
• 化学式: C₁₅H₃₀N₂O₂
• 分子量: 270.415
• InChiKey: IUPSIGDAGUFHNO-YUTCNCBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.27
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  34.06
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2R,3S,6R)-N,2-dimethyl-N-methoxy-6-<<(4-methoxyphenyl)methoxy>methyl>-3-<(triethylsilyl)oxy>octanamide 、 (5S)-5<(4S,6R)-2,2-dimethyl-6-methyl-1,3-dioxan-4-yl>-2-hexanone dimethylhydrazone 生成 (Z)-(2S,8R,9S,12R)-5-(2,2-dimethylhydrazino)-12-<<(4-methoxyphenyl)methoxy>methyl>-8-methyl-9-<(triethylsilyl)oxy>-2-<(4R,6S)-2,2,4-trimethyl-1,3-dioxan-6-yl>-5-tetradecen-7-one
  参考文献：
  名称：

  Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon

  摘要：

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).

  DOI：

  10.1021/jo00313a011
• 作为产物：
  描述：

  3-(E)-(2S,3R)-2-methyl-4-hexene-1,3-diol 在 4-二甲氨基吡啶 、 正丁基锂 、 偶氮二异丁腈 、 碘 、 三正丁基氢锡 、 对甲苯磺酸 、 三乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 100.5h， 生成 (5S)-5<(4S,6R)-2,2-dimethyl-6-methyl-1,3-dioxan-4-yl>-2-hexanone dimethylhydrazone
  参考文献：
  名称：

  Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon

  摘要：

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).

  DOI：

  10.1021/jo00313a011