(4aR,9S,9aS)-2-Benzyl-9-trimethylsilanyl-hexahydro-7-oxa-2-aza-benzocycloheptene-1,6-dione | 134261-55-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (4aR,9S,9aS)-2-Benzyl-9-trimethylsilanyl-hexahydro-7-oxa-2-aza-benzocycloheptene-1,6-dione
• CAS: 134261-55-5
• 化学式: C₁₉H₂₇NO₃Si
• 分子量: 345.514
• InChiKey: BHQXXZIWTVUUFN-JFIYKMOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.31
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  46.61
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (4aR,9S,9aS)-2-Benzyl-9-trimethylsilanyl-hexahydro-7-oxa-2-aza-benzocycloheptene-1,6-dione 在 盐酸 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 正丁基锂 、 草酰氯 、 二甲基亚砜 、 三乙胺 、 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 反应 46.5h， 生成 [1-[(3R,4S)-1-benzyl-3-ethenylpiperidin-4-yl]-3-(6-methoxyquinolin-4-yl)propan-2-yl] acetate
  参考文献：
  名称：

  The Cinchona alkaloids: a silicon-directed synthesis of some advanced intermediates

  摘要：

  N-Benzylmeroquinene aldehyde (5b) was prepared in 10 steps and 21% overall yield from benzylamine. The key transformations involved a stereoselective Lewis acid catalyzed Diels-Alder reaction to produce bicyclic amide 18, which in turn underwent a regioselective Baeyer-Villager oxidation to produce lactone 20. Acid-catalyzed ring opening with concomitant Peterson olefination afforded the meroquinene skeleton, which was converted in high yield to meroquinene aldehyde via a reduction/oxidation sequence. Treatment of this aldehyde with anions derived from 4-methylquinoline smoothly generated alcohols 23a,b, which on acetylation yielded the advanced Cinchona alkaloid intermediates 24a,b.

  DOI：

  10.1021/jo00015a036
• 作为产物：
  描述：

  (4aS,8S,8aR)-2-Benzyl-8-trimethylsilanyl-hexahydro-isoquinoline-1,6-dione 在 disodium hydrogenphosphate 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 39.0h， 以86%的产率得到(4aR,9S,9aS)-2-Benzyl-9-trimethylsilanyl-hexahydro-7-oxa-2-aza-benzocycloheptene-1,6-dione
  参考文献：
  名称：

  The Cinchona alkaloids: a silicon-directed synthesis of some advanced intermediates

  摘要：

  N-Benzylmeroquinene aldehyde (5b) was prepared in 10 steps and 21% overall yield from benzylamine. The key transformations involved a stereoselective Lewis acid catalyzed Diels-Alder reaction to produce bicyclic amide 18, which in turn underwent a regioselective Baeyer-Villager oxidation to produce lactone 20. Acid-catalyzed ring opening with concomitant Peterson olefination afforded the meroquinene skeleton, which was converted in high yield to meroquinene aldehyde via a reduction/oxidation sequence. Treatment of this aldehyde with anions derived from 4-methylquinoline smoothly generated alcohols 23a,b, which on acetylation yielded the advanced Cinchona alkaloid intermediates 24a,b.

  DOI：

  10.1021/jo00015a036