2-[(1R,3S,5Z,9E,11R,12S,14S,16R,18R,20S,21R,23S)-9-[2-[tert-butyl(dimethyl)silyl]oxyethylidene]-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-8-oxo-2,10,15,22-tetraoxatetracyclo[12.10.0.03,11.016,23]tetracos-5-en-21-yl]ethyl 2,2-dimethylpropanoate | 221388-70-1

• 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,9E,11R,12S,14S,16R,18R,20S,21R,23S)-9-[2-[tert-butyl(dimethyl)silyl]oxyethylidene]-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-8-oxo-2,10,15,22-tetraoxatetracyclo[12.10.0.03,11.016,23]tetracos-5-en-21-yl]ethyl 2,2-dimethylpropanoate
• CAS: 221388-70-1
• 化学式: C₅₄H₈₂O₉Si₂
• 分子量: 931.411
• InChiKey: HJXVLWXUOBQVJW-CWORDAEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.65
• 重原子数：
  65
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  98.8
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2-[(1R,3S,5Z,9E,11R,12S,14S,16R,18R,20S,21R,23S)-9-[2-[tert-butyl(dimethyl)silyl]oxyethylidene]-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-8-oxo-2,10,15,22-tetraoxatetracyclo[12.10.0.03,11.016,23]tetracos-5-en-21-yl]ethyl 2,2-dimethylpropanoate 在 hydrido(triphenylphosphine)copper(I) hexamer 作用下， 以 苯 为溶剂， 反应 72.0h， 以70%的产率得到
  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：

  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 、 aluminum amalgam 、 四丙基高钌酸铵 、 4 A molecular sieve 、 水 、 氧气 、 tetraphenylporphyrin 、 双(三甲基硅烷基)氨基钾 、 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 为溶剂， 反应 10.25h， 生成 2-[(1R,3S,5Z,9E,11R,12S,14S,16R,18R,20S,21R,23S)-9-[2-[tert-butyl(dimethyl)silyl]oxyethylidene]-20-[tert-butyl(diphenyl)silyl]oxy-12,16,18-trimethyl-8-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 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

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.