(E)-1-(1,3-benzodioxol-5-yl)-6-[tert-butyl(dimethyl)silyl]oxyhex-2-en-1-one | 207115-79-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: (E)-1-(1,3-benzodioxol-5-yl)-6-[tert-butyl(dimethyl)silyl]oxyhex-2-en-1-one
• CAS: 207115-79-5
• 化学式: C₁₉H₂₈O₄Si
• 分子量: 348.514
• InChiKey: YVZZREBXXNVBNK-VQHVLOKHSA-N

物化性质

• 沸点：
  429.508±45.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.047±0.06 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.96
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  (E)-1-(1,3-benzodioxol-5-yl)-6-[tert-butyl(dimethyl)silyl]oxyhex-2-en-1-one 在 盐酸 、 四氧化锇 、 正丁基锂 、 N-甲基吲哚酮 、 草酰氯 、 4 Angstroem MS 、 四丁基氟化铵 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 水 、 叔丁醇 为溶剂， 反应 47.92h， 生成 (3aR*,4R*,5R*,7aS*)-octahydro-1-methyl-4,5-dihydroxy-3a-(3,4-methylenedioxy)phenylindole
  参考文献：
  名称：

  Assembly of 3a-Arylperhydroindoles by the Intramolecular Cycloaddition of 2-Azaallyl Anions with Alkenes. Total Syntheses of (±)-Crinine, (±)-6-Epicrinine, (−)-Amabiline, and (−)-Augustamine

  摘要：

  The 2-azaallyl anion route to pyrrolidines was used for the concise synthesis of alkaloids featuring the 3a-arylperhydroindole nucleus. The brevity and efficiency of the syntheses described are particularly notable. The key transformations involved the tin-lithium exchange of (2-azaallyl)stannanes to 2-azaallyl anions, which participated in intramolecular [pi 4s + pi 2s] cycloadditions with styrenes to produce the requisite 3a-arylperhydroindoles. (+/-)-Crinine was synthesized in eight steps in 20% overall yield, with the key cycloaddition producing a single stereoisomer of the perhydroindole in 80% yield. (+/-)-6-Epicrinine was an intermediate in this synthesis. The key cycloaddition involved the use of a diene as the anionophile. The first asymmetric syntheses of (-)-amabiline and (-)-augustamine were accomplished in overall yields of 43% (in eight steps) and 42% (in nine steps), respectively, confirming or determining the absolute stereochemistry of the natural products. The key cycloadditions produced the perhydroindoles in 83% and 74% yields, respectively, with reasonable stereocontrol. The highly stereoselective cycloaddition leading to a trans-dialkoxyperhydroindole in 75% yield was consistent with stereochemical predictions. These studies contribute to a growing body of knowledge on the scope and stereochemistry of 2-azaallyl anion cycloadditions.

  DOI：

  10.1021/jo972255+
• 作为产物：
  描述：

  胡椒酸酰氯 、 1-(tert-butyldimethylsilyloxy)-4-pentyne 在 trans-benzyl(chloro)-bis(triphenylphosphine)palladium(II) 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 生成 (E)-1-(1,3-benzodioxol-5-yl)-6-[tert-butyl(dimethyl)silyl]oxyhex-2-en-1-one
  参考文献：
  名称：

  Assembly of 3a-Arylperhydroindoles by the Intramolecular Cycloaddition of 2-Azaallyl Anions with Alkenes. Total Syntheses of (±)-Crinine, (±)-6-Epicrinine, (−)-Amabiline, and (−)-Augustamine

  摘要：

  The 2-azaallyl anion route to pyrrolidines was used for the concise synthesis of alkaloids featuring the 3a-arylperhydroindole nucleus. The brevity and efficiency of the syntheses described are particularly notable. The key transformations involved the tin-lithium exchange of (2-azaallyl)stannanes to 2-azaallyl anions, which participated in intramolecular [pi 4s + pi 2s] cycloadditions with styrenes to produce the requisite 3a-arylperhydroindoles. (+/-)-Crinine was synthesized in eight steps in 20% overall yield, with the key cycloaddition producing a single stereoisomer of the perhydroindole in 80% yield. (+/-)-6-Epicrinine was an intermediate in this synthesis. The key cycloaddition involved the use of a diene as the anionophile. The first asymmetric syntheses of (-)-amabiline and (-)-augustamine were accomplished in overall yields of 43% (in eight steps) and 42% (in nine steps), respectively, confirming or determining the absolute stereochemistry of the natural products. The key cycloadditions produced the perhydroindoles in 83% and 74% yields, respectively, with reasonable stereocontrol. The highly stereoselective cycloaddition leading to a trans-dialkoxyperhydroindole in 75% yield was consistent with stereochemical predictions. These studies contribute to a growing body of knowledge on the scope and stereochemistry of 2-azaallyl anion cycloadditions.

  DOI：

  10.1021/jo972255+