chloro(hex-4-enyloxy)acetic acid methyl ester | 161254-70-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: chloro(hex-4-enyloxy)acetic acid methyl ester
• 英文别名: Methyl 2-((E)-4-hexen-1-oxy)-2-chloroacetate；methyl 2-chloro-2-[(E)-hex-4-enoxy]acetate
• CAS: 161254-70-2
• 化学式: C₉H₁₅ClO₃
• 分子量: 206.669
• InChiKey: BRZBUNDLOXRCJX-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  chloro(hex-4-enyloxy)acetic acid methyl ester 在 (t-BuO)2 作用下， 以 二氯甲烷 为溶剂， 反应 0.83h， 生成 (2R*,3R*)-3-<1-<(ethoxythiocarbonyl)sulfanyl>ethyl>tetrahydropyran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Xanthate Transfer Cyclization of Glycolic Acid-Derived Radicals. Synthesis of Five- to Eight-Membered Ring Ethers

  摘要：

  A novel method for the preparation of functionalized five- to eight-membered ring ethers is described. This method involves the xanthate transfer radical cyclization of 2-(alken-1-oxy)-2-[(ethoxythio-carbonyl)sulfanyl]acetic acid methyl esters 6 to give good yields of xanthate-substituted five- to eight-membered ethers 7 and/or 8, depending on the length of the carbon chain. These cyclic ethers are usually obtained as mixtures of diastereomers. The cyclizations are performed at 150-160 degrees C in tert-butylbenzene with di-tert-butyl peroxide as the initiator. This group-transfer radical cyclization was successfully applied in a total synthesis of lauthisan (44). The use of benzoyl xanthate (56) as a catalyst allows a visible light-induced xanthate transfer cyclization to a tetrahydrofuran in high yield.

  DOI：

  10.1021/jo00101a027
• 作为产物：
  描述：

  4-己烯-1-醇 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 乙酰氯 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 chloro(hex-4-enyloxy)acetic acid methyl ester
  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

文献信息

• 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.
• Xanthate Transfer Cyclization of Glycolic Acid-Derived Radicals. Synthesis of Five- to Eight-Membered Ring Ethers
  作者：Jan H. Udding、J. P. M. Giesselink、Henk Hiemstra、W. Nico Speckamp

  DOI：10.1021/jo00101a027

  日期：1994.11

  A novel method for the preparation of functionalized five- to eight-membered ring ethers is described. This method involves the xanthate transfer radical cyclization of 2-(alken-1-oxy)-2-[(ethoxythio-carbonyl)sulfanyl]acetic acid methyl esters 6 to give good yields of xanthate-substituted five- to eight-membered ethers 7 and/or 8, depending on the length of the carbon chain. These cyclic ethers are usually obtained as mixtures of diastereomers. The cyclizations are performed at 150-160 degrees C in tert-butylbenzene with di-tert-butyl peroxide as the initiator. This group-transfer radical cyclization was successfully applied in a total synthesis of lauthisan (44). The use of benzoyl xanthate (56) as a catalyst allows a visible light-induced xanthate transfer cyclization to a tetrahydrofuran in high yield.