4-O-[(2S,3R,6S,8R,9S)-3-butyl-8-[(2E,4E,6S,7S)-6-[tert-butyl(dimethyl)silyl]oxy-8-hydroxy-3,7-dimethylocta-2,4-dienyl]-9-methyl-2-[(1E,3E)-3-methyl-5-oxo-5-(2-trimethylsilylethoxy)penta-1,3-dienyl]-1,7-dioxaspiro[5.5]undecan-3-yl] 1-O-(2-trimethylsilylethyl) butanedioate | 757192-10-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-O-[(2S,3R,6S,8R,9S)-3-butyl-8-[(2E,4E,6S,7S)-6-[tert-butyl(dimethyl)silyl]oxy-8-hydroxy-3,7-dimethylocta-2,4-dienyl]-9-methyl-2-[(1E,3E)-3-methyl-5-oxo-5-(2-trimethylsilylethoxy)penta-1,3-dienyl]-1,7-dioxaspiro[5.5]undecan-3-yl] 1-O-(2-trimethylsilylethyl) butanedioate
• CAS: 757192-10-2
• 化学式: C₅₀H₉₀O₁₀Si₃
• 分子量: 935.515
• InChiKey: HMKPFCIQVGTSDK-NRJHGOETSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.11
• 重原子数：
  63
• 可旋转键数：
  28
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  127
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  4-O-[(2S,3R,6S,8R,9S)-3-butyl-8-[(2E,4E,6S,7S)-6-[tert-butyl(dimethyl)silyl]oxy-8-hydroxy-3,7-dimethylocta-2,4-dienyl]-9-methyl-2-[(1E,3E)-3-methyl-5-oxo-5-(2-trimethylsilylethoxy)penta-1,3-dienyl]-1,7-dioxaspiro[5.5]undecan-3-yl] 1-O-(2-trimethylsilylethyl) butanedioate 在 四丁基氟化铵 、 戴斯-马丁氧化剂 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 单(3-丁基-8-(9-羧基-6-羟基-3,7-二甲基-2,4,8-壬三烯基)-2-(4-羧基-3-甲基-1,3-丁二烯基)-9-甲基-1,7-二氧杂螺(5.5)十一碳-3-基)丁二酸酯
  参考文献：
  名称：

  Total Synthesis of (−)-Reveromycin A

  摘要：

  The asymmetric total synthesis of (-)-reveromycin A is described. The key steps involved a Lewis acid catalyzed inverse electron demand hetero-Diels-Alder reaction followed by hydroboration/oxidation to afford the spiroketal core 4 in a highly stereoselective manner and introduction of the C18 hemisuccinate by high-pressure acylation.

  DOI：

  10.1021/ol048811l
• 作为产物：
  描述：

  (2E,4E)-6-[(2R,3S,6S,8S,9R)-9-Butyl-9-(tert-butyl-dimethyl-silanyloxy)-8-ethynyl-3-methyl-1,7-dioxa-spiro[5.5]undec-2-yl]-4-methyl-hexa-2,4-dienal 在 bis-triphenylphosphine-palladium(II) chloride N-乙基哌啶 、 咪唑 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 tin(II) trifluoromethanesulfonate 、 四丁基氟化铵 、 三正丁基氢锡 、 氟化氢吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 、 水 为溶剂， 50.0~60.0 ℃ 、400.0 MPa 条件下， 生成 4-O-[(2S,3R,6S,8R,9S)-3-butyl-8-[(2E,4E,6S,7S)-6-[tert-butyl(dimethyl)silyl]oxy-8-hydroxy-3,7-dimethylocta-2,4-dienyl]-9-methyl-2-[(1E,3E)-3-methyl-5-oxo-5-(2-trimethylsilylethoxy)penta-1,3-dienyl]-1,7-dioxaspiro[5.5]undecan-3-yl] 1-O-(2-trimethylsilylethyl) butanedioate
  参考文献：
  名称：

  Total Synthesis of (−)-Reveromycin A

  摘要：

  The asymmetric total synthesis of (-)-reveromycin A is described. The key steps involved a Lewis acid catalyzed inverse electron demand hetero-Diels-Alder reaction followed by hydroboration/oxidation to afford the spiroketal core 4 in a highly stereoselective manner and introduction of the C18 hemisuccinate by high-pressure acylation.

  DOI：

  10.1021/ol048811l

文献信息

• Total Synthesis of (-)-Reveromycin A via a Hetero-Diels-Alder Approach
  作者：Mark Rizzacasa、Mariana El Sous、Danny Ganame、Peter Tregloan

  DOI：10.1055/s-0030-1258308

  日期：2010.12

  The asymmetric total synthesis of (-)-reveromycin A is described which utilizes a Lewis acid catalyzed inverse electron demand­ hetero-Diels-Alder reaction followed by hydroboration/oxidation to afford the labile [6,6]-spiroketal core in a highly stereo­selective manner. An asymmetric syn-aldol reaction installed the stereochemistry at C4-C5 whilst a Stille cross coupling was utilized to form the C21-C22 bond. The C18 hemisuccinate was formed by high pressure acylation reaction and a final Wittig extension followed by global deprotection with tetrabutylammonium fluo­ride gave (-)-reveromycin A.

  (-)-reveromycin A的不对称全合成方法如下：首先通过Lewis酸催化的反向电子需求杂-Diels-Alder反应，接着进行氢硼化/氧化反应，高立体选择性地获得不稳定的[6,6]-螺内酯核心结构。通过不对称顺式醛醇反应确定C4-C5的立体化学结构，而利用Stille交叉偶联反应形成C21-C22键。通过高压酰化反应形成C18半琥珀酸酯，最后进行Wittig扩展和四丁基氟化铵的全保护基去保护，得到(-)-reveromycin A。
• Total Synthesis of (−)-Reveromycin A
  作者：Mariana El Sous、Danny Ganame、Peter A. Tregloan、Mark A. Rizzacasa

  DOI：10.1021/ol048811l

  日期：2004.8.1

  The asymmetric total synthesis of (-)-reveromycin A is described. The key steps involved a Lewis acid catalyzed inverse electron demand hetero-Diels-Alder reaction followed by hydroboration/oxidation to afford the spiroketal core 4 in a highly stereoselective manner and introduction of the C18 hemisuccinate by high-pressure acylation.