diethyl (2S,3S)-4,4-(ethylidenedioxy)-2,3-dihydroxyhept-5-enedioate | 228249-62-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl (2S,3S)-4,4-(ethylidenedioxy)-2,3-dihydroxyhept-5-enedioate
• 英文别名: ethyl (2S,3S)-3-[2-[(E)-3-ethoxy-3-oxoprop-1-enyl]-1,3-dioxolan-2-yl]-2,3-dihydroxypropanoate
• CAS: 228249-62-5
• 化学式: C₁₃H₂₀O₈
• 分子量: 304.297
• InChiKey: NUCFLERLGCIHED-PZIAFJOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  diethyl (2S,3S)-4,4-(ethylidenedioxy)-2,3-dihydroxyhept-5-enedioate 在 2,6-二甲基吡啶 、 四氧化锇 、 重铬酸吡啶 、 4 A molecular sieve 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 作用下， 以 四氯化碳 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 36.08h， 生成 ethyl (2S,3S,5S,6S)-2,3,5,6-tetrakis-<(t-butyl)dimethylsilyloxy>-4,4-ethylenedioxy-7-oxoheptanoate
  参考文献：
  名称：

  Total, asymmetric synthesis of ethyl d-ido-4-heptulosuronate derivatives starting from diethyl 4-oxopimelate

  摘要：

  Bromination of diethyl 4-oxopimelate, followed by double elimination of HBr and ketalization provided diethyl (E,E)-4,4-(ethylidenedioxy)hepta-2,5-dienedioate 4. Sharpless asymmetric dihydroxylation of 4 produced diethyl (2S,3S)-4,4-(ethylidenedioxy)-2,3-dihydroxyhept-5-eneiodate (+)-5, with 78% e.e. The corresponding tetrol could not be obtained in one step. Silylation of (+)-5 and a second asymmetric dihydroxylation, followed by silylation led to 20% of meso-diester 9 and 60% of diethyl (2S,3S,5S,6S)-2,3,5,6-tetrakis[(t-butyl) 4,4-(ethylidenedioxy)heptanedioate (-)-10. Reductive desymmetrization of (-)-10 with DIBAL-H furnished, after selective oxidation, ethyl (2S,3S,5S,6S)-2,3,5,6-tetrakis-[(t-butyl oxoheptanoate (+)-13 which was then converted into ethyl 1,2,3,6-0-tetraacetyl-4,4-ethylidenedioxy-alpha- and beta-D-ido-heptapyranuronate (-)-15 alpha,beta and into the corresponding 3-(alpha-D-pyranosyl)propene (-)-16. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00120-2
• 作为产物：
  描述：

  4-氧代庚二酸二乙酯 在 四氧化锇 、 三氟甲磺酸三甲基硅酯 、 溴 、 N-甲基吗啉氧化物 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 三乙胺 作用下， 以 四氯化碳 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 23.58h， 生成 diethyl (2S,3S)-4,4-(ethylidenedioxy)-2,3-dihydroxyhept-5-enedioate
  参考文献：
  名称：

  Total, asymmetric synthesis of ethyl d-ido-4-heptulosuronate derivatives starting from diethyl 4-oxopimelate

  摘要：

  Bromination of diethyl 4-oxopimelate, followed by double elimination of HBr and ketalization provided diethyl (E,E)-4,4-(ethylidenedioxy)hepta-2,5-dienedioate 4. Sharpless asymmetric dihydroxylation of 4 produced diethyl (2S,3S)-4,4-(ethylidenedioxy)-2,3-dihydroxyhept-5-eneiodate (+)-5, with 78% e.e. The corresponding tetrol could not be obtained in one step. Silylation of (+)-5 and a second asymmetric dihydroxylation, followed by silylation led to 20% of meso-diester 9 and 60% of diethyl (2S,3S,5S,6S)-2,3,5,6-tetrakis[(t-butyl) 4,4-(ethylidenedioxy)heptanedioate (-)-10. Reductive desymmetrization of (-)-10 with DIBAL-H furnished, after selective oxidation, ethyl (2S,3S,5S,6S)-2,3,5,6-tetrakis-[(t-butyl oxoheptanoate (+)-13 which was then converted into ethyl 1,2,3,6-0-tetraacetyl-4,4-ethylidenedioxy-alpha- and beta-D-ido-heptapyranuronate (-)-15 alpha,beta and into the corresponding 3-(alpha-D-pyranosyl)propene (-)-16. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00120-2

文献信息

• Total, asymmetric synthesis of ethyl d-ido-4-heptulosuronate derivatives starting from diethyl 4-oxopimelate
  作者：Sandrine Lemaire-Audoire、Pierre Vogel

  DOI：10.1016/s0957-4166(99)00120-2

  日期：1999.4

  Bromination of diethyl 4-oxopimelate, followed by double elimination of HBr and ketalization provided diethyl (E,E)-4,4-(ethylidenedioxy)hepta-2,5-dienedioate 4. Sharpless asymmetric dihydroxylation of 4 produced diethyl (2S,3S)-4,4-(ethylidenedioxy)-2,3-dihydroxyhept-5-eneiodate (+)-5, with 78% e.e. The corresponding tetrol could not be obtained in one step. Silylation of (+)-5 and a second asymmetric dihydroxylation, followed by silylation led to 20% of meso-diester 9 and 60% of diethyl (2S,3S,5S,6S)-2,3,5,6-tetrakis[(t-butyl) 4,4-(ethylidenedioxy)heptanedioate (-)-10. Reductive desymmetrization of (-)-10 with DIBAL-H furnished, after selective oxidation, ethyl (2S,3S,5S,6S)-2,3,5,6-tetrakis-[(t-butyl oxoheptanoate (+)-13 which was then converted into ethyl 1,2,3,6-0-tetraacetyl-4,4-ethylidenedioxy-alpha- and beta-D-ido-heptapyranuronate (-)-15 alpha,beta and into the corresponding 3-(alpha-D-pyranosyl)propene (-)-16. (C) 1999 Elsevier Science Ltd. All rights reserved.