4(S)-ethyl-4,5-dihydroxypentanal acetonide | 121464-74-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4(S)-ethyl-4,5-dihydroxypentanal acetonide
• 英文别名: (4S)-4-ethyl-4,5-dihydroxypentanal acetonide；3-[(4S)-4-ethyl-2,2-dimethyl-1,3-dioxolan-4-yl]propanal
• CAS: 121464-74-2
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: ZAEKHBVPIUDODJ-JTQLQIEISA-N

物化性质

• 沸点：
  239.6±15.0 °C(Predicted)
• 密度：
  0.947±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4(S)-ethyl-4,5-dihydroxypentanal acetonide 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 0.25h， 生成 (3aS,4S)-methyl 3-benzyl-2,3,3a,4,5,7-hexahydro-4-<(2S)-2-ethyl-2,3-dihydroxypropyl>-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
  参考文献：
  名称：

  Enantioselective syntheses of vinblastine, leurosidine, vincovaline and 20'-epi-vincovaline

  摘要：

  The binary indole-indoline alkaloids vinblastine (1), leurosidine (13), 20'-epi-vincovaline (14a), and vincovaline (14b) were obtained by coupling of vindoline (3) to the tetracyclic intermediates 7a, 7b or 22a, 22b, followed by reduction and cyclization steps (60% overall yield for these reactions). The intermediates were obtained by enantioselective establishment of C20' through a first-step Sharpless oxidation (10a,b) and followed by a subsequent diastereomeric separation (20a,b or 21a,b). Alternatively, enantioselective control of the key secodine-type cyclization in the reaction sequence provided the tetracyclic intermediates 54 and 60 for coupling to vindoline. Selective generation of the natural (1, 13, 14a,b) or unnatural (30, 34, 35a,b) atropisomeric forms of the alkaloids was achieved through alternative closures of ring D'. The natural products were also obtained from the higher energy atropisomers by conformational inversion on heating. For the vinblastine synthesis, the overall yield was 22%.

  DOI：

  10.1021/jo00002a008
• 作为产物：
  描述：

  (2S)-2-ethyl-2-hydroxyhex-5-enol 在 对甲苯磺酸 、 臭氧 、 三苯基膦 作用下， 以 丙酮 为溶剂， 反应 36.25h， 生成 4(S)-ethyl-4,5-dihydroxypentanal acetonide
  参考文献：
  名称：

  Enantioselective syntheses of vinblastine, leurosidine, vincovaline and 20'-epi-vincovaline

  摘要：

  The binary indole-indoline alkaloids vinblastine (1), leurosidine (13), 20'-epi-vincovaline (14a), and vincovaline (14b) were obtained by coupling of vindoline (3) to the tetracyclic intermediates 7a, 7b or 22a, 22b, followed by reduction and cyclization steps (60% overall yield for these reactions). The intermediates were obtained by enantioselective establishment of C20' through a first-step Sharpless oxidation (10a,b) and followed by a subsequent diastereomeric separation (20a,b or 21a,b). Alternatively, enantioselective control of the key secodine-type cyclization in the reaction sequence provided the tetracyclic intermediates 54 and 60 for coupling to vindoline. Selective generation of the natural (1, 13, 14a,b) or unnatural (30, 34, 35a,b) atropisomeric forms of the alkaloids was achieved through alternative closures of ring D'. The natural products were also obtained from the higher energy atropisomers by conformational inversion on heating. For the vinblastine synthesis, the overall yield was 22%.

  DOI：

  10.1021/jo00002a008

文献信息

• Syntheses of 5a‘-<i>h</i><i>omo</i>-Vinblastine and Congeners Designed to Establish Structural Determinants for Isolation of Atropisomers
  作者：Martin E. Kuehne、Scott D. Cowen、Feng Xu、Linda S. Borman

  DOI：10.1021/jo000249z

  日期：2001.8.1

  The syntheses of 5a'-homo-vinblastine (3a) and its C-20' methyl congener 62a were achieved. In contrast to vinblastine, these compounds did not allow isolation of atropisomers because of their lower conformational inversion barrier. However, annelation of a six-membered ring to the conformationally mobile D'-piperidine ring provided an isolated atropisomer 81a, which could be converted to its lower energy conformation 65a on heating. The 5a'-homo-vinblastine congeners 3a, 62a, and 65a showed vinblastine-like inhibition of tubulin polymerization and cytotoxicity to L1210 leukemia cells, albeit at lower potency for the latter activity, than that found with the corresponding compounds in the vinblastine series.
• An Alternative Enantioselective Generation of Intermediates in the Total Synthesis of Vinblastine:  Enantioselection in Secodine-Type Reactions Induced by α-Ferrocenylethyl <i>N</i>-Substituents
  作者：Martin E. Kuehne、Upul K. Bandarage

  DOI：10.1021/jo951857v

  日期：1996.1.1
• KUEHNE, MARTIN
  作者：KUEHNE, MARTIN

  DOI：——

  日期：——
• KUEHNE, MARTIN E.;MATSON, PATRICIA A.;BORNMANN, WILLIAM G., J. ORG. CHEM., 56,(1991) N, C. 513-528
  作者：KUEHNE, MARTIN E.、MATSON, PATRICIA A.、BORNMANN, WILLIAM G.

  DOI：——

  日期：——
• Enantioselective syntheses of vinblastine, leurosidine, vincovaline and 20'-epi-vincovaline
  作者：Martin E. Kuehne、Patricia A. Matson、William G. Bornmann

  DOI：10.1021/jo00002a008

  日期：1991.1

  The binary indole-indoline alkaloids vinblastine (1), leurosidine (13), 20'-epi-vincovaline (14a), and vincovaline (14b) were obtained by coupling of vindoline (3) to the tetracyclic intermediates 7a, 7b or 22a, 22b, followed by reduction and cyclization steps (60% overall yield for these reactions). The intermediates were obtained by enantioselective establishment of C20' through a first-step Sharpless oxidation (10a,b) and followed by a subsequent diastereomeric separation (20a,b or 21a,b). Alternatively, enantioselective control of the key secodine-type cyclization in the reaction sequence provided the tetracyclic intermediates 54 and 60 for coupling to vindoline. Selective generation of the natural (1, 13, 14a,b) or unnatural (30, 34, 35a,b) atropisomeric forms of the alkaloids was achieved through alternative closures of ring D'. The natural products were also obtained from the higher energy atropisomers by conformational inversion on heating. For the vinblastine synthesis, the overall yield was 22%.