(6R,11R)-4-[(2S)-2-[2-[tert-butyl(dimethyl)silyl]oxyethyl]pent-4-enyl]-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-10,10-dimethyl-2-oxaspiro[5.5]undec-4-en-3-one | 1333318-94-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (6R,11R)-4-[(2S)-2-[2-[tert-butyl(dimethyl)silyl]oxyethyl]pent-4-enyl]-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-10,10-dimethyl-2-oxaspiro[5.5]undec-4-en-3-one
• CAS: 1333318-94-7
• 化学式: C₃₂H₆₀O₄Si₂
• 分子量: 564.997
• InChiKey: NIPYSVCOHCQXLL-PEIKUDQGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  38
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (6R,11R)-4-[(2S)-2-[2-[tert-butyl(dimethyl)silyl]oxyethyl]pent-4-enyl]-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-10,10-dimethyl-2-oxaspiro[5.5]undec-4-en-3-one 在 samarium diiodide 、 四丁基硫酸氢铵 、 四丁基碘化铵 、 戴斯-马丁氧化剂 、 对甲苯磺酸 、 N,N-二异丙基乙胺 、 lithium bromide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 8.78h， 生成 (2'R,4S,4aR,5R,7S,8aR)-2'-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(methoxymethoxy)-3',3'-dimethyl-7-prop-2-enylspiro[4a,5,6,7,8,8a-hexahydro-3H-isochromene-4,1'-cyclohexane]-1-one
  参考文献：
  名称：

  A Unified Strategy to ent-Kauranoid Natural Products: Total Syntheses of (−)-Trichorabdal A and (−)-Longikaurin E

  摘要：

  The first total syntheses of (-)-trichorabdal A and (-)-longikaurin E are reported. A unified synthetic strategy is employed that relies on a Pd-mediated oxidative cyclization of a silyl ketene acetal to generate an all-carbon quaternary center and build the bicyclo[3.2.1]octane framework. These studies, taken together with our previous synthesis of (-)-maoecrystal Z, demonstrate that three architecturally distinct ent-kauranoids can be prepared from a common spirolactone intermediate.

  DOI：

  10.1021/ja406599a
• 作为产物：
  描述：

  在 双氧水 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 1.5h， 生成 (6R,11R)-4-[(2S)-2-[2-[tert-butyl(dimethyl)silyl]oxyethyl]pent-4-enyl]-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-10,10-dimethyl-2-oxaspiro[5.5]undec-4-en-3-one
  参考文献：
  名称：

  A unified strategy for the synthesis of (−)-maoecrystal Z, (−)-trichorabdal A, and (−)-longikaurin E

  摘要：

  DOI：

  10.1016/j.tet.2014.03.071

文献信息

• A Unified Strategy to <i>ent</i>-Kauranoid Natural Products: Total Syntheses of (−)-Trichorabdal A and (−)-Longikaurin E
  作者：John T. S. Yeoman、Victor W. Mak、Sarah E. Reisman

  DOI：10.1021/ja406599a

  日期：2013.8.14

  The first total syntheses of (-)-trichorabdal A and (-)-longikaurin E are reported. A unified synthetic strategy is employed that relies on a Pd-mediated oxidative cyclization of a silyl ketene acetal to generate an all-carbon quaternary center and build the bicyclo[3.2.1]octane framework. These studies, taken together with our previous synthesis of (-)-maoecrystal Z, demonstrate that three architecturally distinct ent-kauranoids can be prepared from a common spirolactone intermediate.
• A Concise Total Synthesis of (−)-Maoecrystal Z
  作者：Jacob Y. Cha、John T. S. Yeoman、Sarah E. Reisman

  DOI：10.1021/ja2073356

  日期：2011.9.28

  The first total synthesis of (-)-maoecrystal Z is described. The key steps of the synthesis include a diastereoselective Ti(III)-mediated reductive epoxide coupling reaction and a diastereoselective Sm(II)-mediated reductive cascade cydization reaction. These transformations enabled the preparation of (-)-maoecrystal Z in only 12 steps from (-)-gamma-cyclogeraniol.
• A unified strategy for the synthesis of (−)-maoecrystal Z, (−)-trichorabdal A, and (−)-longikaurin E
  作者：John T.S. Yeoman、Jacob Y. Cha、Victor W. Mak、Sarah E. Reisman

  DOI：10.1016/j.tet.2014.03.071

  日期：2014.7