Methyl 2-(3-buten-1-oxy)-2-acetoxyacetate | 251294-19-6

• 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-(3-buten-1-oxy)-2-acetoxyacetate
• 英文别名: methyl O-(3-butenyl)-α-acetoxyglycolate；methyl 2-acetoxy-2-(3-buten-1-oxy)acetate；Methyl 2-acetyloxy-2-but-3-enoxyacetate
• CAS: 251294-19-6
• 化学式: C₉H₁₄O₅
• 分子量: 202.207
• InChiKey: NGBVAYGLTGHFDI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 2-(3-buten-1-oxy)-2-acetoxyacetate 在 盐酸 、 2,2'-联吡啶 、 乙酰氯 、 copper(l) chloride 作用下， 以 乙醚 、 1,2-二氯乙烷 为溶剂， 反应 48.5h， 生成 cis-methyl 3-chloromethyl-2-tetrahydrofurancarboxylate
  参考文献：
  名称：

  酶解拆分顺式-3-氯甲基-2-四氢呋喃甲酸甲酯

  摘要：

  通过酶催化水解在中性条件下的动力学拆分成功地应用于外消旋顺式-3-氯甲基-2-四氢呋喃甲酸甲酯（1）。用酰基转移酶-I（E = 51）和α-胰凝乳蛋白酶（E = 28）可获得最高的选择性。在两种情况下回收的光学活性甲酯均为（+）-（2 S，3 R）-1。在反应条件下，水解产物自发地环化成双环内酯（-）3a R，6a R）-9，其在一次重结晶后对映体纯。（-）- 9的X射线晶体结构分析 允许确定其绝对配置

  DOI：

  10.1016/s0957-4166(00)86087-5
• 作为产物：
  描述：

  乙酸酐 、 But-3-enyloxy-hydroxy-acetic acid methyl ester 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 3.0h， 生成 Methyl 2-(3-buten-1-oxy)-2-acetoxyacetate
  参考文献：
  名称：

  酶解拆分顺式-3-氯甲基-2-四氢呋喃甲酸甲酯

  摘要：

  通过酶催化水解在中性条件下的动力学拆分成功地应用于外消旋顺式-3-氯甲基-2-四氢呋喃甲酸甲酯（1）。用酰基转移酶-I（E = 51）和α-胰凝乳蛋白酶（E = 28）可获得最高的选择性。在两种情况下回收的光学活性甲酯均为（+）-（2 S，3 R）-1。在反应条件下，水解产物自发地环化成双环内酯（-）3a R，6a R）-9，其在一次重结晶后对映体纯。（-）- 9的X射线晶体结构分析 允许确定其绝对配置

  DOI：

  10.1016/s0957-4166(00)86087-5

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.
• π-Cyclizations of α-methoxycarbonyl oxycarbenium ions; synthesis of oxacyclic carboxylic esters
  作者：Lucie D.M. Lolkema、Henk Hiemstra、Cindy Semeyn、W.Nico Speckamp

  DOI：10.1016/s0040-4020(01)85238-8

  日期：1994.1

  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 .
• Enzymatic resolution of α-acetoxyethers: A new approach to the synthesis of homochiral O,O-acetals
  作者：Sarah J. Fletcher、Christopher M. Rayner

  DOI：10.1016/s0040-4039(99)01483-5

  日期：1999.9

  A variety of alpha-acetoxyethers can be prepared by addition of an alcohol to a glyoxylate and ill situ acetylation using acetyl chloride. They can then be resolved using Pseudomonas fluorescens lipase. Selectivity is highly dependent on the substrate, with high enantiomeric excesses achieved in most cases, with some notable exceptions. Use of alternative lipase enzymes helps overcome such limitations. (C) 1999 Elsevier Science Ltd. All rights reserved.
• 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.