methyl 2-(((tert-butoxycarbonyl)oxy)(3-methoxyphenyl)methyl)acrylate | 1228338-45-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2-(((tert-butoxycarbonyl)oxy)(3-methoxyphenyl)methyl)acrylate
• 英文别名: Methyl 2-[(3-methoxyphenyl)-[(2-methylpropan-2-yl)oxycarbonyloxy]methyl]prop-2-enoate；methyl 2-[(3-methoxyphenyl)-[(2-methylpropan-2-yl)oxycarbonyloxy]methyl]prop-2-enoate
• CAS: 1228338-45-1
• 化学式: C₁₇H₂₂O₆
• 分子量: 322.358
• InChiKey: BLWOPAWGPSPUCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2-(((tert-butoxycarbonyl)oxy)(3-methoxyphenyl)methyl)acrylate 在 calcium fluoride 、 水 、 hydroquinidine (anthraquinone-1,4-diyl) diether 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 60.0h， 以83%的产率得到(S)-(+)-methyl 3-hydroxy-2-methylene-3-(3-methoxyphenyl)propanoate
  参考文献：
  名称：

  Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water

  摘要：

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.

  DOI：

  10.1021/jo201096e
• 作为产物：
  描述：

  3-甲氧基苯甲醛 在 三乙烯二胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 methyl 2-(((tert-butoxycarbonyl)oxy)(3-methoxyphenyl)methyl)acrylate
  参考文献：
  名称：

  Synthesis of β-Lactams via Enantioselective Allylation of Anilines with Morita–Baylis–Hillman Carbonates

  摘要：

  通过对苯胺进行对映选择性烯丙基化反应制备富含对映体的β-内酰胺，随后通过碱促进的环化反应得到。所得的3-亚甲基氮杂环丙酮可通过对映选择性官能化反应产生生物活性β-内酰胺类似物。该方法使用接近等摩尔量的起始原料使得该方法高效且简单。

  DOI：

  10.1055/s-0039-1691570

文献信息

• Asymmetric organocatalytic allylic alkylation of Reissert compounds: a facile access to chiral 1,1-disubstituted 1,2-dihydroisoquinolines
  作者：Tian-You Qin、Wei-Wei Liao、Yan-Jing Zhang、Sean Xiao-An Zhang

  DOI：10.1039/c2ob27269e

  日期：——

  The first asymmetric organocatalytic allylic alkylation of 1,2-dihydro-Reissert compounds and Morita–Baylis–Hillman (MBH) carbonates has been developed, which provided a novel protocol to construct enantioenriched functionalized 1,2-dihydroisoquinolines bearing vicinal quaternary and tertiary chiral centers at C-1 position (up to 94% ee, dr > 20 : 1).

  已开发出第一个1,2-二氢-Reissert化合物和森田-贝利斯-希尔曼（MBH）碳酸酯的不对称有机催化烯丙基烷基化，它为构建带有邻位四级和三级手性中心的对映体富集的功能化1,2-二氢异喹啉提供了新的方案在C-1位置（高达94％ee，dr> 20：1）。
• Lewis base-catalyzed cyanation of Morita-Baylis-Hillman carbonates. Synthesis of allylamine derivatives
  作者：Hai Ma、Feng Sui、Qing-He Zhao、Ning Zhang、Yi Sun、Jing Xian、Meng-Jiao Jiao、Yu-ling Liu、Zhi-Min Wang

  DOI：10.1016/j.tetlet.2017.07.038

  日期：2017.8

  DABCO-catalyzed cyanation of MBH carbonates via 1,3-proton shift transfer is reported. The adducts of cyanation are converted in one step to allylic amines derivatives. The salient features of this reaction include readily available starting materials, mild conditions, broad substrate scope, high efficiency and valuable further applications. The process of the 1,3-proton shift transfer was conducted

  据报道，DABCO通过1，3-质子转移转移催化了MBH碳酸酯的氰化反应。一步将氰化加合物转化为烯丙基胺衍生物。该反应的显着特征包括容易获得的起始原料，温和的条件，广泛的底物范围，高效和有价值的进一步应用。1,3-质子转移转移的过程是通过NMR和DFT计算的联合研究进行的。
• Asymmetric Allylic Monofluoromethylation and Methylation of Morita-Baylis-Hillman Carbonates with FBSM and BSM by Cooperative Cinchona Alkaloid/FeCl2 Catalysis
  作者：Tatsuya Furukawa、Jumpei Kawazoe、Wei Zhang、Takayuki Nishimine、Etsuko Tokunaga、Takashi Matsumoto、Motoo Shiro、Norio Shibata

  DOI：10.1002/anie.201103748

  日期：2011.10.4

  yields with high ee values (see scheme, (DHQD)2AQN=hydroquinidine(anthraquinone‐1,4‐diyl) diether). The cooperative catalysis of bis(cinchona alkaloid) and Lewis acid, particularly FeCl2, was effective for these transformations and gave the monofluoromethylation products with over 90 % ee and methylation products with up to 97 % ee.

  共同努力：标题反应以高收率和高ee 值实现（参见方案，（DHQD）2 AQN =对苯二酚（蒽醌-1,4-二基）二醚）。双（金鸡纳生物碱）和路易斯酸，特别是FeCl 2的协同催化对于这些转化是有效的，并给出了具有超过90％ee的单氟 甲基化产物和具有高达97％ee的甲基化产物 。
• Organocatalytic Enantioselective Allylic Etherification of Morita–Baylis–Hillman Carbonates and Silanols
  作者：Hui-Li Liu、Ming-Sheng Xie、Gui-Rong Qu、Hai-Ming Guo

  DOI：10.1021/acs.joc.6b01931

  日期：2016.10.21

  The organocatalytic asymmetric allylic etherification reaction of Morita–Baylis–Hillman carbonates and silanols was reported for the first time. With modified cinchona alkaloid (DHQD)2PYR as the catalyst, a series of aromatic, heterocyclic, or aliphatic Morita–Baylis–Hillman carbonates (25 examples) worked well with triphenylsilanol, affording the corresponding products in moderate to good yields (up

  首次报道了森田-贝利斯-希尔曼碳酸盐和硅烷醇的有机催化不对称烯丙基醚化反应。以修饰的金鸡纳生物碱（DHQD）2 PYR为催化剂，一系列芳族，杂环或脂肪族Morita-Baylis-Hillman碳酸盐（25个实例）与三苯基硅烷醇效果很好，从而提供了中等至良好收率的相应产品（高达98 ％），高区域选择性（> 20：1）和良好的对映选择性（最高92％）。当使用二甲基苯基硅烷醇作为亲核试剂时，以60％的收率和87％的ee获得产物。
• Synthesis of Chiral α-Trifluoromethylamines with 2,2,2-Trifluoroethylamine as a “Building Block”
  作者：Xiaoyuan Li、Jinhuan Su、Zhourujun Liu、Yuanyuan Zhu、Zhenghao Dong、Shuai Qiu、Jiayi Wang、Li Lin、Zhiqiang Shen、Wenjin Yan、Kairong Wang、Rui Wang

  DOI：10.1021/acs.orglett.5b03566

  日期：2016.3.4

  a cinchonine derived alkaloid, catalyzed asymmetric SN2′–SN2′ reaction between N-2,2,2-trifluoroethylisatin ketimines and MBH type carbonates was realized in a simple and efficient way. A series of chiral α-trifluoromethylamines were prepared with excellent yields and stereoselectivities. A subsequent and easy process of deprotection gave γ-trifluoromethyl-α-methylenelactam in a stereoselective manner

  通过简单有效的方法，实现了由辛可宁衍生的生物碱β-异cupreidine催化的N -2,2,2-三氟乙基异丁酮酮与MBH型碳酸盐之间的不对称S N 2'–S N 2'反应。制备了一系列具有优异收率和立体选择性的手性α-三氟甲基胺。随后且容易的脱保护过程以立体选择性的方式得到了γ-三氟甲基-α-亚甲基内酰胺。