methyl (Z)-2-chloromethyl-3-(1-naphthyl)propenoate | 682350-79-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: methyl (Z)-2-chloromethyl-3-(1-naphthyl)propenoate
• 英文别名: methyl (Z)-2-chloromethyl-3-(1-naphthyl)prop-2-enoate；methyl (Z)-2-(chloromethyl)-3-naphthalen-1-ylprop-2-enoate
• CAS: 682350-79-4
• 化学式: C₁₅H₁₃ClO₂
• 分子量: 260.72
• InChiKey: DEMTVJOCEBBTIZ-UKTHLTGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl (Z)-2-chloromethyl-3-(1-naphthyl)propenoate 在 四丁基溴化铵 Chiralcel OD-H 作用下， 以 四氢呋喃 、 正己烷 、 异丙醇 为溶剂， 反应 0.42h， 生成 (R)-methyl 2-methylene-3-(1-naphthyl)pentanoate
  参考文献：
  名称：

  Expedient synthesis of β,β-disubstituted α-methylenepropionates

  摘要：

  Baylis-Hillman alcohols are excellent sources of the allylic halides ArCH=CH(CH2X)(CO2R) (X = Br. Cl: R-1= Me, Et. Bu'). The Z double bond isomers are attained in high isomeric purity (> 14: 1. ZIE). The halides are chemo- and regiospecifically transformed into the acrylates (ArCHR2)C(=CH2)(CO2R1) on treatment with Zn(R-2)(2) (R-2 =Me. Et, CH2TMS, CH(2)SiMe(2)Ome) or PrZnBr- in the presence of catalytic amounts of copper(1) salts (0.5-20 mol%) in high yield. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.12.002
• 作为产物：
  描述：

  1-萘丙酸,b-羟基-a-亚甲基-,甲基酯 在 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 以76%的产率得到methyl (Z)-2-chloromethyl-3-(1-naphthyl)propenoate
  参考文献：
  名称：

  使用PPh 3 / Cl 3 CCONH 2 †轻度高效地氯化Baylis-Hillman加合物

  摘要：

  通过在室温下用PPh 3 / Cl 3 CCONH 2处理，从Baylis-Hillman加合物获得了一种新的且方便的立体选择合成（Z）-2-（氯甲基）alk-2-enoates的方法。合成可以在温和且无酸的条件下进行，从而以高收率形成产物。

  DOI：

  10.1002/hlca.200790211

文献信息

• Mapping the Mechanism of Nickel-Ferrophite Catalysed Methylation of Baylis-Hillman-Derived S_N2′ Electrophiles
  作者：Andrew Novak、Maria José Calhorda、Paulo Jorge Costa、Simon Woodward

  DOI：10.1002/ejoc.200801029

  日期：2009.2

  presence of ferrophite ligands has been investigated computationally and experimentally. The sense and degree of enantioselectivity attained is independent of both the leaving group and the isomeric structure of the initial allylic halide. DFT studies support the selective formation of a limited number of energetically favoured anti and syn π-allyl intermediates. The observed regio- and enantioselectivity

  已经通过计算和实验研究了在亚铁盐配体存在下对 Baylis-Hillman 衍生的烯丙基亲电试剂的对映选择性 Ni 催化甲基化。获得的对映选择性的意义和程度与离去基团和初始烯丙基卤化物的异构结构无关。DFT 研究支持选择性形成有限数量的能量有利的反和顺 π-烯丙基中间体。观察到的区域选择性和对映选择性可以基于这些结构的能量学进行合理化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Enantioselective Preparation of ?,?-Disubstituted ?-Methylenepropionates by MAO Promotion of the Zinc Schlenk Equilibrium
  作者：Paul J. Goldsmith、Simon J. Teat、Simon Woodward

  DOI：10.1002/anie.200463028

  日期：2005.4.8
• Convenient and efficient stereoselective synthesis of (2Z)-2-(chloromethyl)alk-2-enoates using iron(III) or indium(III) chloride
  作者：Biswanath Das、Joydeep Banerjee、Nasi Ravindranath、Bollu Venkataiah

  DOI：10.1016/j.tetlet.2004.01.101

  日期：2004.3

  The stereoselective synthesis of (2Z)-2-(chloromethyl)alk-2-enoates has been achieved efficiently and in high yields and in short reaction times from Baylis-Hillman adducts, 3-hydroxy-2-methylene-alkanoates, by treatment with FeCl3 or InCl3 at room temperature. (C) 2004 Elsevier Ltd. All rights reserved.
• Expedient synthesis of β,β-disubstituted α-methylenepropionates
  作者：Kallolmay Biswas、Christoph Börner、Josepe Gimeno、Paul J. Goldsmith、Daniella Ramazzotti、Angela L.K. So、Simon Woodward

  DOI：10.1016/j.tet.2004.12.002

  日期：2005.2

  Baylis-Hillman alcohols are excellent sources of the allylic halides ArCH=CH(CH2X)(CO2R) (X = Br. Cl: R-1= Me, Et. Bu'). The Z double bond isomers are attained in high isomeric purity (> 14: 1. ZIE). The halides are chemo- and regiospecifically transformed into the acrylates (ArCHR2)C(=CH2)(CO2R1) on treatment with Zn(R-2)(2) (R-2 =Me. Et, CH2TMS, CH(2)SiMe(2)Ome) or PrZnBr- in the presence of catalytic amounts of copper(1) salts (0.5-20 mol%) in high yield. (C) 2004 Elsevier Ltd. All rights reserved.
• A Mild and Efficient Method for Chlorination ofBaylis–Hillman Adducts Using PPh3/Cl3CCONH2
  作者：Biswanath Das、Nikhil Chowdhury、Kongara Damodar、Bommena Ravikanth

  DOI：10.1002/hlca.200790211

  日期：2007.10

  A new and convenient stereoselective synthesis of (Z)-2-(chloromethyl)alk-2-enoates has been achieved from Baylis–Hillman adducts by treatment with PPh3/Cl3CCONH2 at room temperature. The synthesis can proceed under mild and acid-free conditions to form the products in high yields.

  通过在室温下用PPh 3 / Cl 3 CCONH 2处理，从Baylis-Hillman加合物获得了一种新的且方便的立体选择合成（Z）-2-（氯甲基）alk-2-enoates的方法。合成可以在温和且无酸的条件下进行，从而以高收率形成产物。