Methyl 2-((Z)-3-hexen-1-oxy)-2-acetoxyacetate | 121223-16-3

• 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: Methyl 2-((Z)-3-hexen-1-oxy)-2-acetoxyacetate
• 英文别名: methyl 2-acetoxy-2-(3-(Z)-hexen-1-oxy)acetate；methyl 2-acetyloxy-2-[(Z)-hex-3-enoxy]acetate
• CAS: 121223-16-3
• 化学式: C₁₁H₁₈O₅
• 分子量: 230.261
• InChiKey: FQLISRDUYCWSNO-WAYWQWQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.42
• 重原子数：
  16.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Methyl 2-((Z)-3-hexen-1-oxy)-2-acetoxyacetate 在 Cu(bpy)Cl 盐酸 、 lithium hydroxide 、 乙酰氯 作用下， 以 甲醇 、 乙醚 、 水 、 1,2-二氯乙烷 为溶剂， 反应 34.5h， 生成 (1R*,5R*,6R*)-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：

  叶醇 、 乙酸酐 、 methyl glyoxylate hydrate 在 吡啶 、 4-二甲氨基吡啶 作用下， 生成 Methyl 2-((Z)-3-hexen-1-oxy)-2-acetoxyacetate
  参考文献：
  名称：

  π-Cyclizations of α-methoxycarbonyl oxycarbenium ions; synthesis of oxacyclic carboxylic esters

  摘要：

  Acid-mediated cyclization reactions are described of seven methyl 2-acetoxy-2-(3-alken-1-oxy)acetates with different chain substitution. The major product of the tin tetrachloride-induced cyclization reaction is in most cases a tetrahydropyran containing an equatorial carbomethoxy function at C2 and an axial chlorine atom at C4. The mechanism of its formation involves a net cis-addition of the intermediate alpha-ester oxycarbenium ion to the carbon-carbon double bond, most likely caused by a quasi axial orientation of the ester function in a chair-like transition state. The results are interpreted by invoking (1) the occurrence of a 2-oxonia-Cope rearrangement and (2) the participation of the ester function in the mechanism of cyclization by trapping the cyclic cationic intermediate. The cyclizations of two methyl 2-acetoxy-2-(4-alken-1-oxy)acetates and two methyl 2-acetoxy-2-(alkynoxy)acetates are also described .

  DOI：

  10.1016/s0040-4020(01)85238-8

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。
• Synthesis of oxacyclic carboxylic esters by way of methoxycarbonyloxonium ions; Evidence for a cationic oxa-cope rearrangement
  作者：Lucie D.M. Lolkema、Henk Hiemstra、Hendrik H. Mooiweer、W.Nico Speckamp

  DOI：10.1016/s0040-4039(00)82348-5

  日期：1988.1
• LOLKEMA, LUCIE D. M.;HIEMSTRA, HENK;MOOIWEER, HENDRIK H.;SPECKAMP, W. NIC+, TETRAHEDRON LETT., 29,(1988) N 48, C. 6365-6368
  作者：LOLKEMA, LUCIE D. M.、HIEMSTRA, HENK、MOOIWEER, HENDRIK H.、SPECKAMP, W. NIC+

  DOI：——

  日期：——