1-bromo-2-ethoxy-4-hexyl-3-oxa-5-hexene | 166884-76-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-bromo-2-ethoxy-4-hexyl-3-oxa-5-hexene
• 英文别名: 3-(2-Bromo-1-ethoxyethoxy)non-1-ene
• CAS: 166884-76-0
• 化学式: C₁₃H₂₅BrO₂
• 分子量: 293.244
• InChiKey: WJJWMPWTORECIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  16
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-bromo-2-ethoxy-4-hexyl-3-oxa-5-hexene 在 三氟化硼乙醚 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 trans-4-((E)-3-carbethoxy-2-propenyl)-5-hexyltetrahydrofuran-2-one
  参考文献：
  名称：

  一种新的镍催化碳羰基化立体选择性合成取代的四氢呋喃和丁内酯

  摘要：

  2-碘-和2-溴乙基烯丙基醚经过高度非对映选择性的闭环反应，生成反式-4,5-二取代的内酯。与氧化后米氯过苯甲酸，反式-4,5-二取代的丁内酯（2-呋喃酮）前进以令人满意的总收率（45-56％;> 99％反式）各类取代的前体1（R 2 =苯基，ñ -己基或我-丙基）。使用环状2-碘缩醛作为闭环的前体会导致新的双环杂环，如6a和6b，具有高的内选择性（> 96％内）。一个还报道了吡咯烷的内选择性制备（内> 96％），尽管在这种情况下，由于锌的反应性低，只能有效地通过氘解法捕集中间体锌试剂。

  DOI：

  10.1016/s0040-4039(00)74404-2
• 作为产物：
  描述：

  1-壬烯-3-醇 、 乙烯基乙醚 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以77%的产率得到1-bromo-2-ethoxy-4-hexyl-3-oxa-5-hexene
  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 substituted tetrahydrofurans and butyrolactones by a new nickel catalyzed carbozincation
  作者：Andrea Vaupel、Paul Knochel

  DOI：10.1016/s0040-4039(00)74404-2

  日期：1994.11

  trans-4,5-disubstituted butyrolactones (2-furanones) proceeds in satisfactory overall yield (45–56 %; >99% trans) for a range of substituted precursors 1 (R2 = phenyl, n-hexyl or i-propyl). The use of cyclic 2-iodoacetals as precursors for the ring closure leads to new bicyclic heterocycles, such as 6a and 6b, with high endo-selectivity (>96% endo). An endo-selective preparation of a pyrrolidine is

  2-碘-和2-溴乙基烯丙基醚经过高度非对映选择性的闭环反应，生成反式-4,5-二取代的内酯。与氧化后米氯过苯甲酸，反式-4,5-二取代的丁内酯（2-呋喃酮）前进以令人满意的总收率（45-56％;> 99％反式）各类取代的前体1（R 2 =苯基，ñ -己基或我-丙基）。使用环状2-碘缩醛作为闭环的前体会导致新的双环杂环，如6a和6b，具有高的内选择性（> 96％内）。一个还报道了吡咯烷的内选择性制备（内> 96％），尽管在这种情况下，由于锌的反应性低，只能有效地通过氘解法捕集中间体锌试剂。
• 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.