(2R,4aR,6S,7R,9Z,11aS)-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-[1,3]dioxino[5,4-b]oxonin-7-ol | 193970-47-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (2R,4aR,6S,7R,9Z,11aS)-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-[1,3]dioxino[5,4-b]oxonin-7-ol
• CAS: 193970-47-7
• 化学式: C₂₄H₃₈O₅Si
• 分子量: 434.648
• InChiKey: QHNUBRKRSSBSBZ-CAJGVRPYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.98
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,4aR,6S,7R,9Z,11aS)-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-[1,3]dioxino[5,4-b]oxonin-7-ol 在 六甲基磷酰三胺 、 四丁基氟化铵 、 水 、 双氧水 、 三乙胺 、 三氯氧磷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.67h， 生成 (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
  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：

  methyl (E,5S,6R)-5,6,7-trihydroxyhept-2-enoate 在 Lindlar's catalyst 、 四(三苯基膦)钯 咪唑 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium dihydrogenphosphate 、 5,10,15,20-tetrakisphenylporphyrin 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 2-甲基-2-丁烯 、 hydrido(triphenylphosphine)copper(I) hexamer 、 四丁基氟化铵 、 水 、 氢气 、 氧气 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 臭氧 、 三乙胺 、 三苯基膦 、 lithium chloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 、 苯 为溶剂， 反应 64.99h， 生成 (2R,4aR,6S,7R,9Z,11aS)-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-[1,3]dioxino[5,4-b]oxonin-7-ol
  参考文献：
  名称：

  Nicolaou; Wallace, Paul A.; Shi, Shuhao, Chemistry - A European Journal, 1999, vol. 5, # 2, p. 618 - 627

  摘要：

  DOI：

文献信息

• New Synthetic Technology for the Construction of 9-Membered Ring Cyclic Ethers. Construction of the EFGH Ring Skeleton of Brevetoxin A
  作者：K. C. Nicolaou、Z. Yang、M. Ouellette、G.-Q. Shi、P. Gärtner、J. L. Gunzner、K. A. Agrios、R. Huber、R. Chadha、D. H. Huang

  DOI：10.1021/ja971219p

  日期：1997.8.1
• 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.
• Nicolaou; Wallace, Paul A.; Shi, Shuhao, Chemistry - A European Journal, 1999, vol. 5, # 2, p. 618 - 627
  作者：Nicolaou、Wallace, Paul A.、Shi, Shuhao、Ouellette, Michael A.、Bunnage, Mark E.、Gunzner, Janet L.、Agrios, Konstantinos A.、Shi, Guo-Qiang、Gaertner, Peter、Yang, Zhen

  DOI：——

  日期：——