2-(4-甲氧基苯基氨基)乙酸叔丁酯 | 92685-83-1

• 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
• 中文名称: 2-(4-甲氧基苯基氨基)乙酸叔丁酯
• 英文名称: tert-butyl (4-methoxyphenyl)glycinate
• 英文别名: t-butyl N-(4-methoxyphenyl)glycinate；t-butyl-N-(4-methoxyphenyl)glycinate；tert-butyl 2-(4-methoxyanilino)acetate
• CAS: 92685-83-1
• 化学式: C₁₃H₁₉NO₃
• mdl: MFCD12567523
• 分子量: 237.299
• InChiKey: WQGFJWIQOLOBSM-UHFFFAOYSA-N

物化性质

• 沸点：
  336.2±22.0 °C(Predicted)
• 密度：
  1.083±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.461
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(4-甲氧基苯基氨基)乙酸叔丁酯 在 dirhodium tetraacetate 吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 甲烷磺酰基叠氮化物 作用下， 以 苯 为溶剂， 生成 6-tert-butoxy-2-carbomethoxy-4-(p-methoxyphenyl)-3-oxo-2H-1,4-oxazine
  参考文献：
  名称：

  Dirhodium tetraacetate catalyzed carbon-hydrogen insertion reaction in N-substituted .alpha.-carbomethoxy-.alpha.-diazoacetanilides and structural analogs. Substituent and conformational effects

  摘要：

  A series of acyclic alpha-carbomethoxy-alpha-diazoacetanilides with different N-substituents, 5a-k, was prepared and the rhodium(II) acetate catalyzed reactions studied. It was found that the rhodium carbenoid reaction with these compounds occurred only at the N-substituent; when the N-substituent is a propargyl group, rhodium carbenoid addition to the triple bond is favored, resulting, ultimately, in the formation of a bicyclic furan derivative 8. With an N-(tert-butyloxycarbonyl)methyl substituent, interception of the rhodium carbenoid by the ester carbonyl oxygen occurred preferentially to give, eventually, 1,4-oxazine derivatives 9 and 9'. For N-alkyl substituents, rhodium carbenoid carbon-hydrogen (C-H) insertion into the alkyl group to give 2-azetidinone and/or 2-pyrrolidinone derivatives was observed. The chemoselectivity of the rhodium carbenoid C-H insertion can be altered by the use of the alpha-acetyl and alpha-phenylsulfonyl substituents. In these cases, exclusive C-H insertion at the N-aryl moiety resulted to give 2(3H)-indolinone products. However, the alpha-substituent effect on the chemoselectivity of the insertion reaction is easily overridden by conformational effects about the amide N-C(O) bond as revealed by the insertion reactions of the conformationally rigid compounds 20a-c. The alpha-substituent effects are reestablished when conformational rigidity is removed, as exemplified by the rhodium carbenoid insertion reactions of compounds 29a,b.

  DOI：

  10.1021/jo00042a018
• 作为产物：
  描述：

  [Allyloxycarbonyl-(4-methoxy-phenyl)-amino]-acetic acid tert-butyl ester 在 palladium diacetate 、 trisodium tris(3-sulfophenyl)phosphine 二乙胺 作用下， 以 乙醚 、 水 为溶剂， 反应 0.75h， 以99%的产率得到2-(4-甲氧基苯基氨基)乙酸叔丁酯
  参考文献：
  名称：

  在水介质中钯催化的反应。有效去除氧和氮中的烯丙氧羰基保护基

  摘要：

  可以通过Pd（0）水溶液催化的烯丙基转移到作为接受亲核试剂的二乙胺上，从烯丙基酯，氨基甲酸酯和碳酸盐中以高收率（70-99％）选择性地顺利脱除烯丙氧羰基（Alloc）部分。该方法已成功用于多种仲胺的脱保护。

  DOI：

  10.1016/s0040-4039(00)60524-5

文献信息

• Stereospecific synthesis of chiral precursors of thienamycin from L-Threonine
  作者：Masao Shiozaki、Noboru Ishida、Tetsuo Hiraoka、Hiroshi Maruyama

  DOI：10.1016/s0040-4020(01)91132-9

  日期：1984.1

  L-Threonine was transformed, stereospecifically, to a versatile β-lactam (5a) in 3 steps. This β-lactam was further converted to a key intermediate (25) for the synthesis of thienamycin and its biologically active analogues. Furthermore, the compound 5a was changed to iodides (18 and 23), cyanides (19 and 24), chloromethylketone (26) and aldehydes (30 and 31) which appear to have a latent potential

  3个步骤将L-苏氨酸立体定向转化为通用的β-内酰胺（5a）。将该β-内酰胺进一步转化为合成噻菌霉素及其生物活性类似物的关键中间体（25）。此外，化合物5a变为碘化物（18和23），氰化物（19和24），氯甲基酮（26）和醛（30和31），它们似乎具有潜在的潜力，可以作为碳青霉烯类化合物的合成前体。
• A Convenient Method for Preparation of α-Imino Carboxylic Acid Derivatives and Application to the Asymmetric Synthesis of Unnatural α-Amino Acid Derivative
  作者：Tsubasa Inokuma、Takahisa Jichu、Kodai Nishida、Akira Shigenaga、Akira Otaka

  DOI：10.1248/cpb.c17-00158

  日期：——

  glycine derivatives for the synthesis of α-imino carboxylic acid derivatives. Using this methodology, utilization of unstable glyoxic acid derivatives was avoided. Furthermore, using this methodology we synthesized novel α-imino carboxylic acid derivatives such as α-imino phenyl ester, perfluoroalkyl etsers, imides, and thioester. The asymmetric Mannich reaction of those novel imine derivatives with 1

  我们在本文中描述了锰（IV）介导的Np-甲氧基苯基（PMP）保护的甘氨酸衍生物的氧化，用于合成α-亚氨基羧酸衍生物。使用这种方法，避免了不稳定的乙二酸衍生物的利用。此外，使用这种方法，我们合成了新型的α-亚氨基羧酸衍生物，例如α-亚氨基苯基酯，全氟烷基酯，酰亚胺和硫代酯。还描述了这些新型亚胺衍生物与1,3-二羰基化合物的不对称曼尼希反应，与使用常规α-亚氨基酯型底物相比，新型α-亚氨基酰亚胺具有更高的化学收率和立体选择性。 。
• Cross-Dehydrogenative Coupling Reactions by Transition-Metal and Aminocatalysis for the Synthesis of Amino Acid Derivatives
  作者：Jin Xie、Zhi-Zhen Huang

  DOI：10.1002/anie.201004940

  日期：2010.12.27

  The direct approach: The title coupling reactions of N‐aryl glycine esters with unmodified ketones occurred smoothly in the presence of tert‐butyl hydroperoxide (TBHP) or 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) under mild conditions (see scheme). The oxidant used for CH activation determined the selectivity of the reactions for a particular type of ketone substrate.

  直接方法：在叔丁基氢过氧化物（TBHP）或2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）的存在下，N-芳基甘氨酸酯与未修饰的酮的标题偶联反应平稳进行）在温和的条件下（请参阅计划）。用于CH活化的氧化剂决定了对于特定类型的酮底物的反应选择性。
• Aerobic Asymmetric Dehydrogenative Cross‐Coupling between Two CH Groups Catalyzed by a Chiral‐at‐Metal Rhodium Complex
  作者：Yuqi Tan、Wei Yuan、Lei Gong、Eric Meggers

  DOI：10.1002/anie.201506273

  日期：2015.10.26

  A sustainable CC bond formation is merged with the catalytic asymmetric generation of one or two stereocenters. The introduced catalytic asymmetric cross‐coupling of two CH groups with molecular oxygen as the oxidant profits from the oxidative robustness of a chiral‐at‐metal rhodium(III) catalyst and exploits an autoxidation mechanism or visible‐light photosensitized oxidation. In the latter case

  可持续的CC键形成与一个或两个立体中心的催化不对称生成合并。引入的两个CH基团与分子氧作为氧化剂的催化不对称交叉偶联得益于手性金属铑（III）催化剂的氧化稳健性，并利用了自氧化机制或可见光光敏氧化。在后一种情况下，该催化剂具有双重功能，即作为手性路易斯酸，用于催化对映选择性烯酸酯化学，同时还用作可见光驱动的光氧化还原催化剂。
• Visible-Light-Induced Charge Transfer Enables C_sp3–H Functionalization of Glycine Derivatives: Access to 1,3-Oxazolidines
  作者：Xiaorong Yang、Yin Zhu、Zhixiang Xie、Ying Li、Yuan Zhang

  DOI：10.1021/acs.orglett.0c00234

  日期：2020.2.21

  visible-light-induced aerobic oxidative [2 + 3] cycloaddition reaction between glycine derivatives and styrene oxides has been disclosed that provides an efficient approach for the rapid synthesis of 1,3-oxazolidines under mild conditions. This photoinduced process is enabled by the formation of an electron donor-acceptor complex between glycine derivatives and benzyl iodides.

  已经公开了甘氨酸衍生物和苯乙烯氧化物之间无光氧化还原催化剂的可见光诱导的需氧氧化[2 + 3]环加成反应，该反应为在温和条件下快速合成1,3-恶唑烷提供了一种有效的方法。通过在甘氨酸衍生物和苄基碘之间形成电子供体-受体复合物，可以实现这种光诱导过程。