(E)-(2R,3S,4S,6R,7R,10S)-2,7-Bis-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-4,6,8,10-tetramethyl-5,11-dioxo-dodec-8-enoic acid allyl ester | 852952-71-7

• 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: (E)-(2R,3S,4S,6R,7R,10S)-2,7-Bis-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-4,6,8,10-tetramethyl-5,11-dioxo-dodec-8-enoic acid allyl ester
• 英文别名: prop-2-enyl (E,2R,3S,4S,6R,7R,10S)-2,7-bis[[tert-butyl(dimethyl)silyl]oxy]-3-methoxy-4,6,8,10-tetramethyl-5,11-dioxododec-8-enoate
• CAS: 852952-71-7
• 化学式: C₃₂H₆₀O₇Si₂
• 分子量: 612.995
• InChiKey: QJSQHEFFWKRGGW-CLPFKIKQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.52
• 重原子数：
  41
• 可旋转键数：
  19
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (E)-(2R,3S,4S,6R,7R,10S)-2,7-Bis-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-4,6,8,10-tetramethyl-5,11-dioxo-dodec-8-enoic acid allyl ester 在 4 A molecular sieve 、 溶剂黄146 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 26.91h， 生成
  参考文献：
  名称：

  Total Synthesis of (+)-13-Deoxytedanolide

  摘要：

  A total synthesis of 13-deoxytedanolide is described. The synthesis features a highly stereoselective fragment assembly aldol reaction of methyl ketone 4 and aldehyde 5 to establish the complete carbon skeleton of the natural product in the form of aldol 15. The facile formation of the remarkably unreactive hemiketal 16 thwarted attempts to elaborate 15 to tedanolide. However, deoxygenation of the C(13)-hydroxyl of 16 provided the 13-deoxy hemiketal 17 that was smoothly elaborated to 13-deoxytedanolide.

  DOI：

  10.1021/ja050729d
• 作为产物：
  描述：

  (2R,3S,4S,5R)-5-[(3,4-dimethoxybenzyl)oxy]-3-methoxy-4-methyl-2-[(tert-butyldimethylsilyl)oxy]heptanal 在 2,6-二甲基吡啶 、 sodium chlorite 、 potassium dihydrogenphosphate 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 四氯化钛 、 N,N-二异丙基乙胺 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 偶氮二甲酸二乙酯 作用下， 以 二氯甲烷 为溶剂， 反应 0.13h， 生成 (E)-(2R,3S,4S,6R,7R,10S)-2,7-Bis-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-4,6,8,10-tetramethyl-5,11-dioxo-dodec-8-enoic acid allyl ester
  参考文献：
  名称：

  Total Synthesis of (+)-13-Deoxytedanolide

  摘要：

  A total synthesis of 13-deoxytedanolide is described. The synthesis features a highly stereoselective fragment assembly aldol reaction of methyl ketone 4 and aldehyde 5 to establish the complete carbon skeleton of the natural product in the form of aldol 15. The facile formation of the remarkably unreactive hemiketal 16 thwarted attempts to elaborate 15 to tedanolide. However, deoxygenation of the C(13)-hydroxyl of 16 provided the 13-deoxy hemiketal 17 that was smoothly elaborated to 13-deoxytedanolide.

  DOI：

  10.1021/ja050729d

文献信息

• Total Syntheses of (+)-Tedanolide and (+)-13-Deoxytedanolide
  作者：Joshua R. Dunetz、Lisa D. Julian、Jason S. Newcom、William R. Roush

  DOI：10.1021/ja8063205

  日期：2008.12.3

  13-deoxytedanolide. This led to the decision to pursue the tedanolide synthesis via C(15)-(S)-epimers, since this stereochemical change would destabilize the hemiketal that plagued the attempted synthesis of tedanolide via C(15)-(R) intermediates. However, use of C(15)-(S)-configured intermediates required that the side-chain epoxide be introduced very late in the synthesis, owing to the ease with which

  描述了强效细胞毒素 (+)-tedanolide (1) 和 (+)-13-deoxytedanolide (2) 的收敛全合成。这些化合物的碳骨架是通过立体选择性醛醇反应组装的，该反应将 C(1)-C(12) 酮片段 5 与 C(13)-C(23) 醛片段 6（对于 13-脱氧泰诺内酯）或 52 （对于泰达内酯）。在通往 (+)-1 和 (+)-2 的过程中遇到了多个障碍，需要非常仔细地选择和协调关键中间体的立体化学和功能。这些问题中的主要问题是半缩酮 33b 和 34 的显着稳定性和缺乏反应性，这阻止了从 aldol 4 完成 tedanolide 合成。成功完成 tedanolide 合成的关键是观察到 13-脱氧半缩酮 36 可以是氧化成 C(11, 15)-二酮 38 生成 13-脱氧泰诺内酯。这导致决定通过 C(15)-(S)-差向异构体进行 tedanolide 合成，因为这种立体化学变化会破坏通过
• An Improved Route to (+)‐Tedanolide and Analysis of Its Subtle Effects Controlling Conformation and Biological Behaviour
  作者：Nina Diaz、Mingzhao Zhu、Gunnar Ehrlich、Ulrike Eggert、Yazh Muthukumar、Florenz Sasse、Markus Kalesse

  DOI：10.1002/chem.201103038

  日期：2012.4.16

  The improved synthesis of the antitumor compound (+)‐tedanolide is described through an aldol coupling of bis‐ketone 7. This modification shortens the synthetic steps in the endgame and provides rapid access to this biologically important natural product. Additionally, it serves as a probe in order to unravel the conformational effects that impede or enable its successful synthesis. Having this way

  通过双酮7的醛醇偶联描述了抗肿瘤化合物（+）-泰诺醇化物的合成方法的改进。这种修饰缩短了最终过程中的合成步骤，并提供了对这种生物学上重要的天然产物的快速访问。此外，它还可以作为探针来揭示阻碍或使其成功合成的构象效应。通过这种方式获得去环氧-萜内酯，其生物学特性出乎意料地揭示了类似于念珠菌皂苷而不是脱氧乙醇胺的作用方式。
• Total Synthesis of (+)-13-Deoxytedanolide
  作者：Lisa D. Julian、Jason S. Newcom、William R. Roush

  DOI：10.1021/ja050729d

  日期：2005.5.1

  A total synthesis of 13-deoxytedanolide is described. The synthesis features a highly stereoselective fragment assembly aldol reaction of methyl ketone 4 and aldehyde 5 to establish the complete carbon skeleton of the natural product in the form of aldol 15. The facile formation of the remarkably unreactive hemiketal 16 thwarted attempts to elaborate 15 to tedanolide. However, deoxygenation of the C(13)-hydroxyl of 16 provided the 13-deoxy hemiketal 17 that was smoothly elaborated to 13-deoxytedanolide.