2-[(1R,3S,5Z,11R,12S,14S,16R,18R,20S,21R,23S)-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-9-oxo-2,10,15,22-tetraoxatetracyclo[12.10.0.03,11.016,23]tetracos-5-en-21-yl]ethyl 2,2-dimethylpropanoate | 221380-85-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 2-[(1R,3S,5Z,11R,12S,14S,16R,18R,20S,21R,23S)-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-9-oxo-2,10,15,22-tetraoxatetracyclo[12.10.0.03,11.016,23]tetracos-5-en-21-yl]ethyl 2,2-dimethylpropanoate
• CAS: 221380-85-4
• 化学式: C₄₆H₆₆O₈Si
• 分子量: 775.111
• InChiKey: RSAAIFFQAOOKTQ-PQPMZUTCSA-N

物化性质

• 沸点：
  768.520±60.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.125±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.09
• 重原子数：
  55
• 可旋转键数：
  10
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-[(1R,3S,5Z,11R,12S,14S,16R,18R,20S,21R,23S)-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-9-oxo-2,10,15,22-tetraoxatetracyclo[12.10.0.03,11.016,23]tetracos-5-en-21-yl]ethyl 2,2-dimethylpropanoate 在 咪唑 、 4-二甲氨基吡啶 、 aluminum amalgam 、 四丙基高钌酸铵 、 hydrido(triphenylphosphine)copper(I) hexamer 、 4 A molecular sieve 、 水 、 氧气 、 tetraphenylporphyrin 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 、 三乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 98.25h， 生成
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 4: Final Stages and Completion

  摘要：

  The total synthesis of brevetoxin A is described, Our methodology of palladium-catalyzed couplings with cyclic ketene acetal phosphates was utilized to functionalize nine-membered ring lactone 4 followed by a [4+2] singlet oxygen addition to the resulting 1,3-diene (6), The product endoperoxide (7) was transformed into coupling partners 3a and 3b to be reacted with aldehyde 2, Our first attempted union of 3a and aldehyde 2 failed, most probably due to steric hindrance, which led us to explore other olefination coupling reactions. Horner- Wittig type coupling was found to be successful on advanced model systems: diphenylphosphine oxides 21 and 28 were each coupled with aldehyde 2. Key intermediates 3b and 2 were successfully coupled and ring F oxocene (44) was cyclized through the hydroxy dithioketal cyclization methodology, The final manipulations were then executed to complete the first total synthesis of brevetoxin A.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<646::aid-chem646>3.0.co;2-e
• 作为产物：
  描述：

  (2S,3R,4S,5aS,6aR,8R,10S,11R,12aS,13aR)-10-(tert-Butyl-diphenyl-silanyloxy)-2,11-bis-(2-hydroxy-ethyl)-4,6a,8-trimethyl-tetradecahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cycloocten-3-ol 在 4-二甲氨基吡啶 、 lithium hydroxide 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 水 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 63.5h， 生成 2-[(1R,3S,5Z,11R,12S,14S,16R,18R,20S,21R,23S)-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-9-oxo-2,10,15,22-tetraoxatetracyclo[12.10.0.03,11.016,23]tetracos-5-en-21-yl]ethyl 2,2-dimethylpropanoate
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 3: Construction of GHIJ and BCDE Ring Systems

  摘要：

  Successful syntheses of highly complex intermediates 2 (GHIJ ring system) and 3 (BCDE ring system) for the total synthesis of brevetoxin A (1) are described. Several of our methodologies were utilized to achieve this goal: i) hydroxy epoxide cyclizations of intermediates 22 and 30 (rings I and H, respectively); ii) hydroxy dithioketal cyclization of 45 (ring G); and, iii) palladium-catalyzed coupling with bis(cyclic ketene acetal phosphate) 68 (rings B and D). With the knowledge gained from our previous model studies, 2 and 3 were expected to be pivotal intermediates on the synthetic route to brevetoxin A.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<628::aid-chem628>3.0.co;2-e

文献信息

• Total Synthesis of Brevetoxin A: Part 4: Final Stages and Completion
  作者：K. C. Nicolaou、Janet L. Gunzner、Guo-qiang Shi、Konstantinos A. Agrios、Peter Gärtner、Zhen Yang

  DOI：10.1002/(sici)1521-3765(19990201)5:2<646::aid-chem646>3.0.co;2-e

  日期：1999.2.1

  The total synthesis of brevetoxin A is described, Our methodology of palladium-catalyzed couplings with cyclic ketene acetal phosphates was utilized to functionalize nine-membered ring lactone 4 followed by a [4+2] singlet oxygen addition to the resulting 1,3-diene (6), The product endoperoxide (7) was transformed into coupling partners 3a and 3b to be reacted with aldehyde 2, Our first attempted union of 3a and aldehyde 2 failed, most probably due to steric hindrance, which led us to explore other olefination coupling reactions. Horner- Wittig type coupling was found to be successful on advanced model systems: diphenylphosphine oxides 21 and 28 were each coupled with aldehyde 2. Key intermediates 3b and 2 were successfully coupled and ring F oxocene (44) was cyclized through the hydroxy dithioketal cyclization methodology, The final manipulations were then executed to complete the first total synthesis of brevetoxin A.
• Total Synthesis of Brevetoxin A: Part 3: Construction of GHIJ and BCDE Ring Systems
  作者：K. C. Nicolaou、Guo-qiang Shi、Janet L. Gunzner、Peter Gärtner、Paul A. Wallace、Michael A. Ouellette、Shuhao Shi、Mark E. Bunnage、Konstantinos A. Agrios、Chris A. Veale、Chan-Kou Hwang、John Hutchinson、C. V. C. Prasad、William W. Ogilvie、Zhen Yang

  DOI：10.1002/(sici)1521-3765(19990201)5:2<628::aid-chem628>3.0.co;2-e

  日期：1999.2.1

  Successful syntheses of highly complex intermediates 2 (GHIJ ring system) and 3 (BCDE ring system) for the total synthesis of brevetoxin A (1) are described. Several of our methodologies were utilized to achieve this goal: i) hydroxy epoxide cyclizations of intermediates 22 and 30 (rings I and H, respectively); ii) hydroxy dithioketal cyclization of 45 (ring G); and, iii) palladium-catalyzed coupling with bis(cyclic ketene acetal phosphate) 68 (rings B and D). With the knowledge gained from our previous model studies, 2 and 3 were expected to be pivotal intermediates on the synthetic route to brevetoxin A.