(6R,11R)-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[(2S)-2-(2-hydroxyethyl)pent-4-enyl]-10,10-dimethyl-2-oxaspiro[5.5]undec-4-en-3-one | 1448616-42-9

• 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)-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[(2S)-2-(2-hydroxyethyl)pent-4-enyl]-10,10-dimethyl-2-oxaspiro[5.5]undec-4-en-3-one
• CAS: 1448616-42-9
• 化学式: C₂₆H₄₆O₄Si
• 分子量: 450.734
• InChiKey: UDDXXVAMWCCFJO-MZEQIWSPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.27
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (6R,11R)-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[(2S)-2-(2-hydroxyethyl)pent-4-enyl]-10,10-dimethyl-2-oxaspiro[5.5]undec-4-en-3-one 在 samarium diiodide 、 四丁基碘化铵 、 戴斯-马丁氧化剂 、 N,N-二异丙基乙胺 、 lithium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 7.28h， 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：

  (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 四丁基硫酸氢铵 、 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 反应 1.5h， 以63%的产率得到(6R,11R)-11-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[(2S)-2-(2-hydroxyethyl)pent-4-enyl]-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 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