(Z)-6-Benzo[1,3]dioxol-5-yl-3-methoxymethoxy-hepta-4,6-dien-1-ol | 160849-84-3

• 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: (Z)-6-Benzo[1,3]dioxol-5-yl-3-methoxymethoxy-hepta-4,6-dien-1-ol
• CAS: 160849-84-3
• 化学式: C₁₆H₂₀O₅
• 分子量: 292.332
• InChiKey: NNHKATYAWKDKIH-HYXAFXHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.36
• 重原子数：
  21.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (Z)-6-Benzo[1,3]dioxol-5-yl-3-methoxymethoxy-hepta-4,6-dien-1-ol 在 盐酸 、 正丁基锂 、 草酰氯 、 4 A molecular sieve 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 35.58h， 生成
  参考文献：
  名称：

  2-氮杂烯丙基阴离子环加成法在合成（±）-可利因和（±）-6-依匹可利因中的应用

  摘要：

  （2-氮杂烯丙基）锡烷9与正丁基锂的金属转移产生2-氮杂烯丙基阴离子12，其与烯烃进行分子内环加成反应，以单一立体异构体的形式以80％的产率得到全氢吲哚10。从10到6-依匹替林2和可丽宁1的转化很容易完成。

  DOI：

  10.1016/0040-4039(94)88457-9
• 作为产物：
  描述：

  5-(1-bromovinyl)benzo[d][1,3]dioxole 在 Lindlar's catalyst 喹啉 、 bis-triphenylphosphine-palladium(II) chloride 、 正丁基锂 、 四丁基氟化铵 、 氢气 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， -78.0~25.0 ℃ 、34.48 kPa 条件下， 反应 6.84h， 生成 (Z)-6-Benzo[1,3]dioxol-5-yl-3-methoxymethoxy-hepta-4,6-dien-1-ol
  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+

文献信息

• Application of the 2-azaallyl anion cycloaddition method to syntheses of (±)-crinine and (±)-6-epicrinine
  作者：William H. Pearson、Frank E. Lovering

  DOI：10.1016/0040-4039(94)88457-9

  日期：1994.12

  Transmetalation of the (2-azaallyl)stannane 9 with n-BuLi produced the 2-azaallyl anion 12 which underwent an intramolecular cycloaddition with an alkene to give the perhydroindole 10 in 80% yield as a single stereoisomer. Transformation of 10 to 6-epicrinine 2 and crinine 1 was readily accomplished.

  （2-氮杂烯丙基）锡烷9与正丁基锂的金属转移产生2-氮杂烯丙基阴离子12，其与烯烃进行分子内环加成反应，以单一立体异构体的形式以80％的产率得到全氢吲哚10。从10到6-依匹替林2和可丽宁1的转化很容易完成。
• Assembly of 3a-Arylperhydroindoles by the Intramolecular Cycloaddition of 2-Azaallyl Anions with Alkenes. Total Syntheses of (±)-Crinine, (±)-6-Epicrinine, (−)-Amabiline, and (−)-Augustamine
  作者：William H. Pearson、Frank E. Lovering

  DOI：10.1021/jo972255+

  日期：1998.5.1

  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.