2-[(1R,3S,9R,10S,12S,14R,16R,18S,19R,21S)-18-[tert-butyl(diphenyl)silyl]oxy-10,14,16-trimethylspiro[2,6,8,13,20-pentaoxatetracyclo[10.10.0.03,9.014,21]docosane-7,1'-cyclohexane]-19-yl]ethyl 2,2-dimethylpropanoate | 205865-04-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧环庚烷
• 英文名称: 2-[(1R,3S,9R,10S,12S,14R,16R,18S,19R,21S)-18-[tert-butyl(diphenyl)silyl]oxy-10,14,16-trimethylspiro[2,6,8,13,20-pentaoxatetracyclo[10.10.0.03,9.014,21]docosane-7,1'-cyclohexane]-19-yl]ethyl 2,2-dimethylpropanoate
• CAS: 205865-04-9
• 化学式: C₄₈H₇₂O₈Si
• 分子量: 805.18
• InChiKey: KLTKNYFIDNQBPN-SSFHJCDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  57
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  81.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-[(1R,3S,9R,10S,12S,14R,16R,18S,19R,21S)-18-[tert-butyl(diphenyl)silyl]oxy-10,14,16-trimethylspiro[2,6,8,13,20-pentaoxatetracyclo[10.10.0.03,9.014,21]docosane-7,1'-cyclohexane]-19-yl]ethyl 2,2-dimethylpropanoate 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 、 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 、 苯 为溶剂， 反应 48.5h， 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
• 作为产物：
  描述：

  环己酮二甲缩酮 在 4-二甲氨基吡啶 、 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 2-[(1R,3S,9R,10S,12S,14R,16R,18S,19R,21S)-18-[tert-butyl(diphenyl)silyl]oxy-10,14,16-trimethylspiro[2,6,8,13,20-pentaoxatetracyclo[10.10.0.03,9.014,21]docosane-7,1'-cyclohexane]-19-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 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.