(Z)-(4S,5aS,6aR,8R,12aS,13aR)-2,11-Bis-(2-benzyloxy-ethyl)-4,6a,8-trimethyl-4,5,5a,6a,7,8,9,12a,13,13a-decahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene | 126694-03-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Z)-(4S,5aS,6aR,8R,12aS,13aR)-2,11-Bis-(2-benzyloxy-ethyl)-4,6a,8-trimethyl-4,5,5a,6a,7,8,9,12a,13,13a-decahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene
• 英文别名: (1R,3S,5S,9R,11S,13Z,16R)-1,5,16-trimethyl-7,13-bis(2-phenylmethoxyethyl)-2,8,12-trioxatricyclo[9.6.0.03,9]heptadeca-6,13-diene
• CAS: 126694-03-9
• 化学式: C₃₅H₄₆O₅
• 分子量: 546.747
• InChiKey: JQKIGRCHYFLMFC-IVDJKZQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (Z)-(4S,5aS,6aR,8R,12aS,13aR)-2,11-Bis-(2-benzyloxy-ethyl)-4,6a,8-trimethyl-4,5,5a,6a,7,8,9,12a,13,13a-decahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene 在 咪唑 、 sodium hydroxide 、 thexylborane 、 水 、 双氧水 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 31.0h， 生成 (2S,3R,4S,5aS,6aR,8R,10S,11R,12aS,13aR)-2,11-Bis-(2-benzyloxy-ethyl)-10-(tert-butyl-diphenyl-silanyloxy)-4,6a,8-trimethyl-tetradecahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cycloocten-3-ol
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 1: First Generation Strategy and Construction of BCD Ring System

  摘要：

  Discussed herein is our first generation strategy for the total synthesis of brevetoxin A. This approach relies upon dissection of the molecule at the nine-membered ring site (ring E), A Wittig coupling of requisite polycyclic fragments 3 and 4 followed by hydroxy dithioketal cyclization was expected to furnish the polycyclic framework of brevetoxin A (1). Intermediate 8 was anticipated to be a valid synthetic precursor to phosphonium salt 3, and its synthesis was accomplished by a bis(lactonization)/thionolactone formation/functionalization sequence. In order to test our synthetic strategy, the synthesis of an advanced model system (36) was attempted. Aldehyde 38 and phosphonium salt 37 were successfully synthesized and coupled through a:Wittig reaction. Unfortunately, the planned hydroxy dithioketal cyclization to form the crucial nonacene (ring E) did not proceed as anticipated and this synthetic approach was discontinued.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<599::aid-chem599>3.0.co;2-n
• 作为产物：
  描述：

  在 palladium dihydroxide 、 palladium on activated charcoal 劳森试剂 、 2,6-二甲基吡啶 、 sodium periodate 、 aluminum amalgam 、 N-氯代丁二酰亚胺 、 四氧化锇 、 2,2'-二硫二吡啶 、 四甲基硫脲 、 2SPh2 、 水 、 氢气 、 silver perchlorate 、 四丁基碘化铵 、 sodium hydride 、 氟化氢吡啶 、 N-甲基吗啉氧化物 、 三苯基膦 、 zinc(II) chloride 、 zinc dibromide 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醚 、 二氯甲烷 、 乙酸乙酯 、 甲苯 、 乙腈 、 paraffin 、 xylene 为溶剂， 反应 59.16h， 生成 (Z)-(4S,5aS,6aR,8R,12aS,13aR)-2,11-Bis-(2-benzyloxy-ethyl)-4,6a,8-trimethyl-4,5,5a,6a,7,8,9,12a,13,13a-decahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 1: First Generation Strategy and Construction of BCD Ring System

  摘要：

  Discussed herein is our first generation strategy for the total synthesis of brevetoxin A. This approach relies upon dissection of the molecule at the nine-membered ring site (ring E), A Wittig coupling of requisite polycyclic fragments 3 and 4 followed by hydroxy dithioketal cyclization was expected to furnish the polycyclic framework of brevetoxin A (1). Intermediate 8 was anticipated to be a valid synthetic precursor to phosphonium salt 3, and its synthesis was accomplished by a bis(lactonization)/thionolactone formation/functionalization sequence. In order to test our synthetic strategy, the synthesis of an advanced model system (36) was attempted. Aldehyde 38 and phosphonium salt 37 were successfully synthesized and coupled through a:Wittig reaction. Unfortunately, the planned hydroxy dithioketal cyclization to form the crucial nonacene (ring E) did not proceed as anticipated and this synthetic approach was discontinued.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<599::aid-chem599>3.0.co;2-n

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.
• New synthetic strategies for the construction of medium size cyclic ethers. Stereocontrolled synthesis of the BCD ring framework of brevetoxin A
  作者：K. C. Nicolaou、D. G. McGarry、P. K. Sommers

  DOI：10.1021/ja00165a085

  日期：1990.4
• NICOLAOU, K. C.;MCGARRY, D. G.;SOMMERS, P. K., J. AMER. CHEM. SOC., 112,(1990) N, C. 3696-3697
  作者：NICOLAOU, K. C.、MCGARRY, D. G.、SOMMERS, P. K.

  DOI：——

  日期：——