methyl 2-acetoxy-2-(3-butyl-1-hexen-1-oxy)acetate | 121223-12-9

• 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: methyl 2-acetoxy-2-(3-butyl-1-hexen-1-oxy)acetate
• 英文别名: Methyl 2-(3-butyn-1-oxy)-2-acetoxyacetate；methyl 2-acetyloxy-2-but-3-ynoxyacetate
• CAS: 121223-12-9
• 化学式: C₉H₁₂O₅
• 分子量: 200.191
• InChiKey: USTRSUCNWZMHFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  14.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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-acetoxy-2-(3-butyl-1-hexen-1-oxy)acetate 在 盐酸 、 乙酰氯 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以91%的产率得到Methyl 2-(3-butyn-1-oxy)-2-chloroacetate
  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：

  乙酸酐 、 methyl glyoxylate hydrate 、 3-丁炔-1-醇 在 吡啶 、 4-二甲氨基吡啶 作用下， 生成 methyl 2-acetoxy-2-(3-butyl-1-hexen-1-oxy)acetate
  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

• 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：——