Methyl 2-<(cyclohex-3-enylmethyl)oxy>-2-acetoxyacetate | 121223-19-6

• 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-<(cyclohex-3-enylmethyl)oxy>-2-acetoxyacetate
• 英文别名: methyl 2-acetoxy-2-(3-cyclohexen-1-methoxy)acetate；methyl 2-acetyloxy-2-(cyclohex-3-en-1-ylmethoxy)acetate
• CAS: 121223-19-6；121223-31-2
• 化学式: C₁₂H₁₈O₅
• 分子量: 242.272
• InChiKey: NKMORCWAUFEECO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.42
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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-<(cyclohex-3-enylmethyl)oxy>-2-acetoxyacetate 在 盐酸 、 偶氮二异丁腈 、 三正丁基氢锡 、 乙酰氯 作用下， 以 乙醚 、 二氯甲烷 、 苯 为溶剂， 反应 3.33h， 生成 (1R*,2S*,5S*)-3-oxabicyclo<3.3.1>nonane-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：

  3-环己烯-1-甲醇 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 Methyl 2-<(cyclohex-3-enylmethyl)oxy>-2-acetoxyacetate
  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

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.
• 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 .
• 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：——