trans-(4R,5S)-5-pentyl-2-butoxytetrahydrofuran-4-carbaldehyde

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: trans-(4R,5S)-5-pentyl-2-butoxytetrahydrofuran-4-carbaldehyde
• 英文别名: (2S,3R)-5-butoxy-2-pentyloxolane-3-carbaldehyde
• 化学式: C₁₄H₂₆O₃
• 分子量: 242.359
• InChiKey: GQTGACBOVIBYNM-RFHHWMCGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  trans-(4R,5S)-5-pentyl-2-butoxytetrahydrofuran-4-carbaldehyde 在 jones reagent 作用下， 以 丙酮 为溶剂， 反应 0.08h， 以90%的产率得到(2S,3R)-(-)-5-oxo-2-pentyltetrahydrofuran-3-carboxylic acid
  参考文献：
  名称：

  Stereoselective Synthesis of Heterocyclic Zinc Reagents via a Nickel-Catalyzed Radical Cyclization

  摘要：

  Unsaturated iodo or bromo acetals of type 2 undergo a smooth cyclization mediated by diethylzinc (2 equiv) and Ni(acac)(2) as catalyst (2-5 mol %). These cyclizations proceed via a radical mechanism affording a (tetrahydrofuranylmethyl)zinc halide of type 1, which can be reacted with various electrophiles after a transmetalation with CuCN . 2LiCl. High stereoselectivities are usually observed in the ring closures, especially if monocyclic cyclization precursors are used. In these cases, bicyclic products of the endo-configuration are obtained with over 94% diastereoselectivity. The synthetic method has been extended to the preparation of a nitrogen heterocycle and over 98% pure trans-4,5-disubstituted gamma-butyrolactones. A short enantioselective synthesis of (-)-methylenolactocine (3) using the radical cyclization and a novel oxidation of alpha-silyl zinc peroxide as a key step is also described.

  DOI：

  10.1021/jo960617s
• 作为产物：
  描述：

  dipentylzinc 在 titanium(IV) isopropylate 、 bis(acetylacetonate)nickel(II) 、 N-溴代丁二酰亚胺(NBS) 、 三甲基氯硅烷 、 c-trans-C₆₁₀(N(H)Tf)2 、 diethylzinc 、 氧气 、 lithium iodide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 21.0h， 生成 trans-(4R,5S)-5-pentyl-2-butoxytetrahydrofuran-4-carbaldehyde
  参考文献：
  名称：

  通过镍催化的分子内碳氧化锌的（-）-甲基内酯短促合成

  摘要：

  内酯2（ - ） -可被转化在一个步骤中进methylenolactocin 1在4个步骤制备，30％总产率和> 92％ee的由（E）起始-3- trimethylsilylpropenal 4。关键步骤是由Et 2 Zn介导的多官能溴-链烯基硅烷3的新的镍催化环化反应。中间有机锌物质7已被氧气直接氧化为醛。

  DOI：

  10.1016/0040-4039(94)02243-5

文献信息

• Stereoselective Synthesis of Heterocyclic Zinc Reagents via a Nickel-Catalyzed Radical Cyclization
  作者：Andrea Vaupel、Paul Knochel

  DOI：10.1021/jo960617s

  日期：1996.1.1

  Unsaturated iodo or bromo acetals of type 2 undergo a smooth cyclization mediated by diethylzinc (2 equiv) and Ni(acac)(2) as catalyst (2-5 mol %). These cyclizations proceed via a radical mechanism affording a (tetrahydrofuranylmethyl)zinc halide of type 1, which can be reacted with various electrophiles after a transmetalation with CuCN . 2LiCl. High stereoselectivities are usually observed in the ring closures, especially if monocyclic cyclization precursors are used. In these cases, bicyclic products of the endo-configuration are obtained with over 94% diastereoselectivity. The synthetic method has been extended to the preparation of a nitrogen heterocycle and over 98% pure trans-4,5-disubstituted gamma-butyrolactones. A short enantioselective synthesis of (-)-methylenolactocine (3) using the radical cyclization and a novel oxidation of alpha-silyl zinc peroxide as a key step is also described.
• A short formal synthesis of (−)-methylenolactocin via a nickel catalyzed intramolecular carbozincation
  作者：Andrea Vaupel、Paul Knochel

  DOI：10.1016/0040-4039(94)02243-5

  日期：1995.1

  The lactone 2 which can be converted in one step into (−)-methylenolactocin 1 was prepared in 4 steps, 30 % overall yield and > 92 % ee starting from (E)-3-trimethylsilylpropenal 4. The key step is a new nickel catalyzed cyclization of the polyfunctional bromo-alkenylsilane 3 mediated by Et2Zn. The intermediate organozinc species 7 has been directly oxidized to an aldehyde with oxygen.

  内酯2（ - ） -可被转化在一个步骤中进methylenolactocin 1在4个步骤制备，30％总产率和> 92％ee的由（E）起始-3- trimethylsilylpropenal 4。关键步骤是由Et 2 Zn介导的多官能溴-链烯基硅烷3的新的镍催化环化反应。中间有机锌物质7已被氧气直接氧化为醛。