methyl 2-(((tert-butoxycarbonyl)oxy)(3-chlorophenyl)methyl)acrylate | 1005192-99-3

• 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-chlorophenyl)methyl)acrylate
• 英文别名: Methyl 2-[(3-chlorophenyl)-[(2-methylpropan-2-yl)oxycarbonyloxy]methyl]prop-2-enoate
• CAS: 1005192-99-3
• 化学式: C₁₆H₁₉ClO₅
• 分子量: 326.777
• InChiKey: HSUNJGJIJKQTGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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-(((tert-butoxycarbonyl)oxy)(3-chlorophenyl)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-chlorophenyl)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：

  4-氯苯甲醛 在 三乙烯二胺 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 methyl 2-(((tert-butoxycarbonyl)oxy)(3-chlorophenyl)methyl)acrylate
  参考文献：
  名称：

  膦催化的[3 + 2]森田-贝利斯-希尔曼碳酸盐与异恶唑基烯烃的环化

  摘要：

  已开发出一种膦催化的森田-贝利斯-希尔曼（MBH）碳酸酯与3-甲基-4-硝基-5-苯乙烯基恶唑的碳酸盐环化反应[3 + 2]，以中等至良好的产率提供各种多功能异恶唑，具有中等至优异的非对映选择性。用螺环手性膦作为催化剂，获得高达89％的ee。

  DOI：

  10.1021/acs.joc.0c01948

文献信息

• Dual Organocatalysis: Asymmetric Allylic-Allylic Alkylation of α,α-Dicyanoalkenes and Morita-Baylis-Hillman Carbonates
  作者：Hai-Lei Cui、Jing Peng、Xin Feng、Wei Du、Kun Jiang、Ying-Chun Chen

  DOI：10.1002/chem.200802534

  日期：2009.2.2

  The first highly enantioselective allylic–allylic alkylation of α,α‐dicyanoalkenes and Morita–Baylis–Hillman carbonates by dual catalysis of (DHQD)2AQN and (S)‐BINOL has been investigated. Excellent stereoselectivities have been achieved for a broad spectrum of substrates (d.r. > 99:1, up to 99 % ee). The multifunctional allylic products could be efficiently converted to a range of complex chiral cyclic

  通过（DHQD）2 AQN和（S）-BINOL的双重催化作用，首次研究了α，α-二氰基烯烃和Morita-Baylis-Hillman碳酸盐的高对映选择性烯丙基-烯丙基烷基化反应。对于广泛的底物（dr> 99：1，高达99％ee），已经实现了出色的立体选择性 。多功能烯丙基产物可以有效地转化为一系列复杂的手性环状骨架。EWG =吸电子基团（DHQD）2 AQN =对苯二酚（蒽醌-1,4-二甲苯基）二醚，（S）-BINOL =（S）-（-）-1,1'-bi-2-萘酚。
• 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 。
• The decarboxylation coupling reaction of α-keto acid with Baylis-Hillman carbonates by visible light photoredox catalysis
  作者：He Zhao、Niannian Ni、Xiaonian Li、Dongping Cheng、Xiaoliang Xu

  DOI：10.1016/j.poly.2021.115337

  日期：2021.9

  Acylation of Baylis-Hillman carbonates by visible light catalysis has been reported. Acyl radical is produced by decarboxylation of α-keto acid. This method has mild conditions, wide substrate scope, good functional group tolerance, and moderate to good yield, which provides a new route for the acylation of Baylis-Hillman derivatives.

  已经报道了通过可见光催化对 Baylis-Hillman 碳酸盐进行酰化。酰基由α-酮酸脱羧产生。该方法条件温和，底物范围广，官能团耐受性好，收率适中，为Baylis-Hillman衍生物的酰化提供了一条新途径。
• Organocatalytic Asymmetric CS Bond Formation: Synthesis of α-Methylene-β-mercapto Esters with Simple Alkyl Thiols
  作者：Aijun Lin、Haibin Mao、Xi Zhu、Huiming Ge、Renxiang Tan、Chengjian Zhu、Yixiang Cheng

  DOI：10.1002/adsc.201100522

  日期：2011.12

  A highly efficient organocatalytic enantioselective CS bond formation reaction between simple alkyl thiols and Morita–Baylis–Hillman (MBH) carbonates is described. The optically active α-methylene β-mercapto esters could be obtained under mild reaction conditions with excellent enantioselectivities (up to 97% ee). The broad scope and simple operation make this methodology very practical.

  描述了简单的烷基硫醇与森田-贝利斯-希尔曼（MBH）碳酸盐之间的高效有机催化对映选择性CS键形成反应。光学活性α -亚甲基β -巯基酯具有优异的对映选择性（高达97％的温和反应条件下可以得到EE）。广泛的范围和简单的操作使这种方法非常实用。