(4S,5aS,6aR,8R,12aS,13aR)-4,6a,8-Trimethyl-dodecahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene-2,11-dione | 126694-00-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S,5aS,6aR,8R,12aS,13aR)-4,6a,8-Trimethyl-dodecahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene-2,11-dione
• 英文别名: (1R,3S,5S,9R,11S,16R)-1,5,16-trimethyl-2,8,12-trioxatricyclo[9.6.0.03,9]heptadecane-7,13-dione
• CAS: 126694-00-6
• 化学式: C₁₇H₂₆O₅
• 分子量: 310.39
• InChiKey: WTPOQAAFYZOVNB-CRJZJDTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4S,5aS,6aR,8R,12aS,13aR)-4,6a,8-Trimethyl-dodecahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene-2,11-dione 在 劳森试剂 、 四甲基硫脲 作用下， 以 xylene 为溶剂， 反应 3.0h， 以63%的产率得到(4S,5aS,6aR,8R,12aS,13aR)-4,6a,8-Trimethyl-dodecahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene-2,11-dithione
  参考文献：
  名称：

  New synthetic strategies for the construction of medium size cyclic ethers. Stereocontrolled synthesis of the BCD ring framework of brevetoxin A

  摘要：

  DOI：

  10.1021/ja00165a085
• 作为产物：
  描述：

  (Z)-(5aS,6aR,8S,12aS,13aR)-4,6a,8-Trimethyl-5,5a,6a,7,8,12a,13,13a-octahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene-2,11-dione 在 palladium on activated charcoal 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以100%的产率得到(4S,5aS,6aR,8R,12aS,13aR)-4,6a,8-Trimethyl-dodecahydro-1,6,12-trioxa-cyclohepta[4,5]benzo[1,2]cyclooctene-2,11-dione
  参考文献：
  名称：

  New synthetic strategies for the construction of medium size cyclic ethers. Stereocontrolled synthesis of the BCD ring framework of brevetoxin A

  摘要：

  DOI：

  10.1021/ja00165a085

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：——
• Total Synthesis of Brevetoxin A: Part 1: First Generation Strategy and Construction of BCD Ring System
  作者：K. C. Nicolaou、Mark E. Bunnage、Daniel G. McGarry、Shuhao Shi、Patricia K. Somers、Paul A. Wallace、Xin-Jie Chu、Konstantinos A. Agrios、Janet L. Gunzner、Zhen Yang

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

  日期：1999.2.1

  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.