cis-3-(1-chloropropyl)-2-tetrahydrofurancarboxylic acid methyl ester | 135718-76-2

• 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: cis-3-(1-chloropropyl)-2-tetrahydrofurancarboxylic acid methyl ester
• 英文别名: (2R*,3S*)-2-Carbomethoxy-3-(1-chloropropyl)tetrahydrofuran；methyl (2R,3S)-3-(1-chloropropyl)oxolane-2-carboxylate
• CAS: 135718-76-2；135718-77-3；135718-97-7；135718-98-8
• 化学式: C₉H₁₅ClO₃
• 分子量: 206.669
• InChiKey: VHDUGTUZYNBQHO-OECOWPMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  cis-3-(1-chloropropyl)-2-tetrahydrofurancarboxylic acid methyl ester 在 lithium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 16.0h， 生成 (1R*,5R*,6R*)-6-Ethyl-2,7-dioxabicyclo<3.3.0>oct-8-one 、 (1R*,5R*,6S*)-6-Ethyl-2,7-dioxabicyclo<3.3.0>oct-8-one
  参考文献：
  名称：

  Transition Metal-Catalyzed, Chlorine-Transfer Radical Cyclizations of 2-(3-Alken-1-oxy)-2-Chloroacetates. Formal Total Synthesis of Avenaciolide and Isoavenaciolide

  摘要：

  A novel method for the synthesis of functionalized tetrahydrofurans is described. This method involves the treatment of 2-(3-alken-1-oxy)-2-chloroacetates 1 with a catalytic amount of Cu(bpy)Cl in refluxing 1,2-dichloroethane to give good yields of 3-(1-chloroalkyl)-2-tetrahydrofuran carboxylic esters 2. The stereochemical course of the radical cyclizations shows a-preference for the formation of 2,3-cis-substituted tetrahydrofurans in all cases. This selectivity is exploited in the formation of bicyclic lactones which form spontaneously upon ester hydrolysis. As an application of this methodology a formal total synthesis of avenaciolide (28) and isoavenaciolide (29) is described.

  DOI：

  10.1021/jo00087a011
• 作为产物：
  描述：

  Methyl 2-((E)-3-hexen-1-oxy)-2-acetoxyacetate 在 copper(l) chloride 盐酸 、 2,2'-联吡啶 、 乙酰氯 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 72.5h， 生成 cis-3-(1-chloropropyl)-2-tetrahydrofurancarboxylic acid methyl ester
  参考文献：
  名称：

  铜催化甘氨酸和乙醇酸衍生物的氯转移环化

  摘要：

  在催化量的氯化亚铜和2,2'-联吡啶的存在下，氯甘氨酸和氯乙醇酸衍生物可在原子转移过程中平稳环化，分别生成官能化的脯氨酸酯和2-四氢呋喃羧酸酯。

  DOI：

  10.1016/0040-4039(91)80706-c

文献信息

• Copper catalyzed chlorine transfer cyclizations of glycine and glycolic acid derivatives
  作者：Jan H. Udding、Henk Hiemstra、Marco N.A. van Zanden、W.Nico Speckamp

  DOI：10.1016/0040-4039(91)80706-c

  日期：1991.6

  Chloroglycine and chloroglycolic acid derivatives smoothly cyclize in the presence of a catalytic amount of cuprous chloride and 2,2′-bipyridine to produce functionalized proline and 2-tetrahydrofurancarboxylic esters, respectively, in an atom transfer process.

  在催化量的氯化亚铜和2,2'-联吡啶的存在下，氯甘氨酸和氯乙醇酸衍生物可在原子转移过程中平稳环化，分别生成官能化的脯氨酸酯和2-四氢呋喃羧酸酯。
• Transition Metal-Catalyzed, Chlorine-Transfer Radical Cyclizations of 2-(3-Alken-1-oxy)-2-Chloroacetates. Formal Total Synthesis of Avenaciolide and Isoavenaciolide
  作者：Jan H. Udding、Kees C. J. M. Tuijp、Marco N. A. van Zanden、Henk Hiemstra、W. Nico Speckamp

  DOI：10.1021/jo00087a011

  日期：1994.4

  A novel method for the synthesis of functionalized tetrahydrofurans is described. This method involves the treatment of 2-(3-alken-1-oxy)-2-chloroacetates 1 with a catalytic amount of Cu(bpy)Cl in refluxing 1,2-dichloroethane to give good yields of 3-(1-chloroalkyl)-2-tetrahydrofuran carboxylic esters 2. The stereochemical course of the radical cyclizations shows a-preference for the formation of 2,3-cis-substituted tetrahydrofurans in all cases. This selectivity is exploited in the formation of bicyclic lactones which form spontaneously upon ester hydrolysis. As an application of this methodology a formal total synthesis of avenaciolide (28) and isoavenaciolide (29) is described.