4-(3,3-dicarbethoxy-2-phenylpropyl)-2-ethoxy-5-hexyltetrahydrofuran

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 4-(3,3-dicarbethoxy-2-phenylpropyl)-2-ethoxy-5-hexyltetrahydrofuran
• 英文别名: diethyl 2-[2-[(2S,3R)-5-ethoxy-2-hexyloxolan-3-yl]-1-phenylethyl]propanedioate
• 化学式: C₂₇H₄₂O₆
• 分子量: 462.627
• InChiKey: RXGXANFUHAWMHI-IIQVAULWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  33
• 可旋转键数：
  17
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-壬烯-3-醇 在 bis(acetylacetonate)nickel(II) N-溴代丁二酰亚胺(NBS) 、 diethylzinc 、 lithium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 36.17h， 生成 4-(3,3-dicarbethoxy-2-phenylpropyl)-2-ethoxy-5-hexyltetrahydrofuran
  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

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.