tert-butyl-(3-methoxymethoxypent-4-ynyloxy)dimethylsilane | 158074-69-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tert-butyl-(3-methoxymethoxypent-4-ynyloxy)dimethylsilane
• 英文别名: tert-butyl-[3-(methoxymethoxy)pent-4-ynoxy]-dimethylsilane
• CAS: 158074-69-2
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: DHWUPNRWCNEDAA-UHFFFAOYSA-N

物化性质

• 沸点：
  277.0±35.0 °C(Predicted)
• 密度：
  0.915±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.02
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl-(3-methoxymethoxypent-4-ynyloxy)dimethylsilane 在 Lindlar's catalyst 盐酸 、 bis-triphenylphosphine-palladium(II) chloride 、 正丁基锂 、 草酰氯 、 4 A molecular sieve 、 四丁基氟化铵 、 氢气 、 二甲基亚砜 、 三乙胺 、 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 50.17h， 生成 (1S,7S,8R)-7-Benzo[1,3]dioxol-5-yl-2-oxa-4-aza-tricyclo[5.2.2.0^4,8]undec-10-ene
  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：

  3-(叔丁基-二甲基-硅烷基OXY)-丙醛 在 正丁基锂 、 四甲基乙二胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 18.67h， 生成 tert-butyl-(3-methoxymethoxypent-4-ynyloxy)dimethylsilane
  参考文献：
  名称：

  Approach to 6a-Epipretazettine and 6a-Epiprecriwelline via an Intramolecular 2-Azaallyl Anion Cycloaddition Reaction

  摘要：

  An intramolecular 2-azaallyl anion cycloaddition with a diene produced the 2,3,4,6,7,7a-hexahydroindol 33 with complete control of relative stereochemistry, thus providing the first example of the e use of such a cycloaddition in an approach to a relatively complex target molecule. The 2-azaallyl anion was generated by tin-lithium exchange of the (2-azaallyl)stannane 32. The stannane was prepared by a convergent route using a Stille coupling of the vinyl bromide 14 with the vinylstannane 28, providing the diene 29. An unexpected isomerization occurred in the Stille coupling. Transformation of the cycloadduct 33 to the allylic methyl ethers 36 and 37 produced potential precursors of 6a-epiprecriwelline (4) and 6a-epipretazettine (3), respectively. The inability to carry out an oxidative desilylation thwarted the completion of the syntheses of these alkaloids.

  DOI：

  10.1021/jo00098a026

文献信息

• METHOD FOR THE PRODUCTION OF MUMBAISTATIN DERIVATIVES
  申请人：SCHWINK Lothar

  公开号：US20090156836A1

  公开（公告）日：2009-06-18

  The present invention relates to a process for preparing mumbaistatin derivatives (I), where the anthraquinone skeleton is constructed via a Diels-Alder reaction and the central methylene bridge via a transition metal-catalyzed reaction, and to the intermediates used in this process.

  本发明涉及一种制备孟买斯塔汀衍生物（I）的方法，其中蒽醌骨架通过Diels-Alder反应构建，中央亚甲基桥通过过渡金属催化反应构建，并涉及用于该过程的中间体。
• Method for the production of mumbaistatin derivatives
  申请人：Sanofi-Aventis

  公开号：US07763740B2

  公开（公告）日：2010-07-27

  The present invention relates to a process for preparing mumbaistatin derivatives (I), where the anthraquinone skeleton is constructed via a Diels-Alder reaction and the central methylene bridge via a transition metal-catalyzed reaction, and to the intermediates used in this process.

  本发明涉及一种制备mumbaistatin衍生物（I）的过程，其中蒽醌骨架通过Diels-Alder反应构建，中央亚甲基桥通过过渡金属催化反应构建，并涉及用于该过程的中间体。
• 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.