(2S,3R,6S,8R,9S)-8-[(2E,4E,6S,7S)-6,8-bis[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethylocta-2,4-dienyl]-3-butyl-2-ethynyl-9-methyl-1,7-dioxaspiro[5.5]undecan-3-ol | 757192-06-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3R,6S,8R,9S)-8-[(2E,4E,6S,7S)-6,8-bis[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethylocta-2,4-dienyl]-3-butyl-2-ethynyl-9-methyl-1,7-dioxaspiro[5.5]undecan-3-ol
• CAS: 757192-06-6
• 化学式: C₃₈H₇₀O₅Si₂
• 分子量: 663.142
• InChiKey: PZQMXPKELNFQRD-ATCHQDRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.17
• 重原子数：
  45
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.84
• 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：

  (2S,3R,6S,8R,9S)-8-[(2E,4E,6S,7S)-6,8-bis[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethylocta-2,4-dienyl]-3-butyl-2-ethynyl-9-methyl-1,7-dioxaspiro[5.5]undecan-3-ol 在 4-二甲氨基吡啶 、 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 为溶剂， 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]-2-ethynyl-9-methyl-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
• 作为产物：
  描述：

  (4E,6E)-(2S,3S)-8-[(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]-2,6-dimethyl-octa-4,6-diene-1,3-diol 在 咪唑 、 四丁基氟化铵 作用下， 生成 (2S,3R,6S,8R,9S)-8-[(2E,4E,6S,7S)-6,8-bis[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethylocta-2,4-dienyl]-3-butyl-2-ethynyl-9-methyl-1,7-dioxaspiro[5.5]undecan-3-ol
  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。