[(2R,3S,4aR,6S,7R,9aS)-7-[(2S,3S,4aR,8aS)-2-(2-Bromo-acetyl)-octahydro-pyrano[3,2-b]pyran-3-yloxy]-3-(tert-butyl-diphenyl-silanyloxy)-2-(tert-butyl-diphenyl-silanyloxymethyl)-octahydro-1,5-dioxa-benzocyclohepten-6-yl]-acetaldehyde | 256441-19-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(2R,3S,4aR,6S,7R,9aS)-7-[(2S,3S,4aR,8aS)-2-(2-Bromo-acetyl)-octahydro-pyrano[3,2-b]pyran-3-yloxy]-3-(tert-butyl-diphenyl-silanyloxy)-2-(tert-butyl-diphenyl-silanyloxymethyl)-octahydro-1,5-dioxa-benzocyclohepten-6-yl]-acetaldehyde
• 英文别名: 2-[(2R,3S,4aR,6S,7R,9aS)-7-[[(2S,3S,4aR,8aS)-2-(2-bromoacetyl)-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-3-yl]oxy]-3-[tert-butyl(diphenyl)silyl]oxy-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,4,4a,6,7,8,9,9a-octahydro-2H-pyrano[3,2-b]oxepin-6-yl]acetaldehyde
• CAS: 256441-19-7
• 化学式: C₅₄H₆₉BrO₉Si₂
• 分子量: 998.211
• InChiKey: GNZJCCMUZMNOBX-CMOPSFDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.86
• 重原子数：
  66
• 可旋转键数：
  17
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  98.8
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  [(2R,3S,4aR,6S,7R,9aS)-7-[(2S,3S,4aR,8aS)-2-(2-Bromo-acetyl)-octahydro-pyrano[3,2-b]pyran-3-yloxy]-3-(tert-butyl-diphenyl-silanyloxy)-2-(tert-butyl-diphenyl-silanyloxymethyl)-octahydro-1,5-dioxa-benzocyclohepten-6-yl]-acetaldehyde 在 咪唑 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 samarium diiodide 、 草酰氯 、 三乙基硼 、 四丁基氟化铵 、 三正丁基氢锡 、 四氯化钛 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 、 苯 为溶剂， 反应 28.42h， 生成 [(1R,3S,5R,10S,12R,15S,17S,19R,22R,24S)-21,21-bis(ethylsulfanyl)-22-(hydroxymethyl)-2,6,11,18,23-pentaoxapentacyclo[15.9.0.03,12.05,10.019,24]hexacosan-15-yl] acetate
  参考文献：
  名称：

  A Convergent Synthesis of the Decacyclic Ciguatoxin Model Containing the F−M Ring Framework

  摘要：

  A highly convergent synthesis of the decacyclic ciguatoxin model 2, which contains the F-M ring framework of the natural product, has been achieved through the assembly of pentacyclic oxonane 4 and JKLM ring fragment 5. The two key steps in the synthesis of the former compound are (i) a Lewis acid-mediated intramolecular reaction of a gamma-alkoxyallylsilane with an acetal group to form an O-linked oxacycle and (ii) a SmI2-mediated intramolecular Reformatsky reaction leading to construction of the annelated oxonane ring system. Preliminary biological investigations revealed that model compound 2 did not inhibit the binding of tritium-labeled dihydrobrevetoxin B to voltage-sensitive sodium channels at micromolar concentrations.

  DOI：

  10.1021/jo990989b
• 作为产物：
  描述：

  在 N-溴代丁二酰亚胺(NBS) 、 草酰氯 、 camphor-10-sulfonic acid 、 三氧化硫吡啶 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 2.08h， 生成 [(2R,3S,4aR,6S,7R,9aS)-7-[(2S,3S,4aR,8aS)-2-(2-Bromo-acetyl)-octahydro-pyrano[3,2-b]pyran-3-yloxy]-3-(tert-butyl-diphenyl-silanyloxy)-2-(tert-butyl-diphenyl-silanyloxymethyl)-octahydro-1,5-dioxa-benzocyclohepten-6-yl]-acetaldehyde
  参考文献：
  名称：

  A Convergent Synthesis of the Decacyclic Ciguatoxin Model Containing the F−M Ring Framework

  摘要：

  A highly convergent synthesis of the decacyclic ciguatoxin model 2, which contains the F-M ring framework of the natural product, has been achieved through the assembly of pentacyclic oxonane 4 and JKLM ring fragment 5. The two key steps in the synthesis of the former compound are (i) a Lewis acid-mediated intramolecular reaction of a gamma-alkoxyallylsilane with an acetal group to form an O-linked oxacycle and (ii) a SmI2-mediated intramolecular Reformatsky reaction leading to construction of the annelated oxonane ring system. Preliminary biological investigations revealed that model compound 2 did not inhibit the binding of tritium-labeled dihydrobrevetoxin B to voltage-sensitive sodium channels at micromolar concentrations.

  DOI：

  10.1021/jo990989b

文献信息

• A Convergent Synthesis of the Decacyclic Ciguatoxin Model Containing the F−M Ring Framework
  作者：Masayuki Inoue、Makoto Sasaki、Kazuo Tachibana

  DOI：10.1021/jo990989b

  日期：1999.12.1

  A highly convergent synthesis of the decacyclic ciguatoxin model 2, which contains the F-M ring framework of the natural product, has been achieved through the assembly of pentacyclic oxonane 4 and JKLM ring fragment 5. The two key steps in the synthesis of the former compound are (i) a Lewis acid-mediated intramolecular reaction of a gamma-alkoxyallylsilane with an acetal group to form an O-linked oxacycle and (ii) a SmI2-mediated intramolecular Reformatsky reaction leading to construction of the annelated oxonane ring system. Preliminary biological investigations revealed that model compound 2 did not inhibit the binding of tritium-labeled dihydrobrevetoxin B to voltage-sensitive sodium channels at micromolar concentrations.