(1S,3R,8R,10S,12R,14R,15S,17R,19R)-15-[tert-butyl(dimethyl)silyl]oxy-17-[3-[tert-butyl(diphenyl)silyl]oxypropyl]-7,7-bis(ethylsulfanyl)-10-methyl-2,9,13,18-tetraoxatetracyclo[10.8.0.03,10.014,19]icosane-8-carbaldehyde | 205864-92-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: (1S,3R,8R,10S,12R,14R,15S,17R,19R)-15-[tert-butyl(dimethyl)silyl]oxy-17-[3-[tert-butyl(diphenyl)silyl]oxypropyl]-7,7-bis(ethylsulfanyl)-10-methyl-2,9,13,18-tetraoxatetracyclo[10.8.0.03,10.014,19]icosane-8-carbaldehyde
• CAS: 205864-92-2
• 化学式: C₄₇H₇₄O₇S₂Si₂
• 分子量: 871.403
• InChiKey: BNBNITZSHLOMKK-MCKIGKLLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.94
• 重原子数：
  58
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  123
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (1S,3R,8R,10S,12R,14R,15S,17R,19R)-15-[tert-butyl(dimethyl)silyl]oxy-17-[3-[tert-butyl(diphenyl)silyl]oxypropyl]-7,7-bis(ethylsulfanyl)-10-methyl-2,9,13,18-tetraoxatetracyclo[10.8.0.03,10.014,19]icosane-8-carbaldehyde 、 (Z)-(2R,4aR,6S,7R,11aS)-6-[2-(Diphenyl-phosphinoyl)-ethyl]-7-(1-methoxy-1-methyl-ethoxy)-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-1,3,5-trioxa-benzocyclononene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以88%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：

  在 咪唑 、 2,6-二甲基吡啶 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 palladium dihydroxide 、 正丁基锂 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 pyridine-SO3 complex 、 4 A molecular sieve 、 四丁基氟化铵 、 氢气 、 三甲基铝 、 silver perchlorate 、 4-甲基苯磺酸吡啶 、 zinc trifluoromethanesulfonate 、 碳酸氢钠 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 、 间氯过氧苯甲酸 、 乙硫醇 作用下， 以 四氢呋喃 、 甲醇 、 硝基甲烷 、 二氯甲烷 、 溶剂黄146 、 二甲基亚砜 、 甲苯 为溶剂， 反应 85.83h， 生成 (1S,3R,8R,10S,12R,14R,15S,17R,19R)-15-[tert-butyl(dimethyl)silyl]oxy-17-[3-[tert-butyl(diphenyl)silyl]oxypropyl]-7,7-bis(ethylsulfanyl)-10-methyl-2,9,13,18-tetraoxatetracyclo[10.8.0.03,10.014,19]icosane-8-carbaldehyde
  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.