tert-butyl (4-(trifluoromethyl)benzyl)carbamate | 1264670-40-7

• 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: tert-butyl (4-(trifluoromethyl)benzyl)carbamate
• 英文别名: tert-butyl N-[[4-(trifluoromethyl)phenyl]methyl]carbamate
• CAS: 1264670-40-7
• 化学式: C₁₃H₁₆F₃NO₂
• 分子量: 275.271
• InChiKey: CMRMOLQLRCAYFR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl (4-(trifluoromethyl)benzyl)carbamate 在 4-二甲氨基吡啶 、 水 、 氧气 、 Selectfluor 、 10-甲基-9-均三甲苯基吖啶高氯酸盐 作用下， 以 乙腈 为溶剂， 以84 %的产率得到对三氟甲基苯甲醛
  参考文献：
  名称：

  腈、醇和胺的 C(sp3)−C 和 C(sp3)−N 键的无金属可见光诱导氧化裂解

  摘要：

  这项工作提出了使用 Acr + -Mes/Selectflu/DMAP 系统和 O 对腈、醇（二醇）和胺的无张力 C−C(sp 3 ) 和 C−N(sp 3 ) 键进行可见光介导的氧化裂解2作为氧化剂。

  DOI：

  10.1002/chem.202303295
• 作为产物：
  描述：

  N-(tert-butoxycarbonyl)-α-(tributylstannyl)-4-trifluoromethylbenzylamine 在 二氧化碳 、 cesium fluoride 、 盐酸 作用下， 以 N,N-二甲基甲酰胺 、 乙醚 、 水 为溶剂， 100.0 ℃ 、1.0 MPa 条件下， 反应 3.0h， 以99%的产率得到tert-butyl (4-(trifluoromethyl)benzyl)carbamate
  参考文献：
  名称：

  Synthesis of Arylglycine and Mandelic Acid Derivatives through Carboxylations of α-Amido and α-Acetoxy Stannanes with Carbon Dioxide

  摘要：

  Incorporation reactions of carbon dioxide (CO2) with N-Boc-alpha\-amido and a-acetoxy stannanes were developed using CsF as a mild tin activator. Monoprotected alpha-amido stannanes could be used, and the corresponding arylglycine derivatives were obtained in moderate-to-high yields under 1 MPa (10 atm) of CO2 pressure. alpha-Acetoxy stannanes also underwent carboxylation to afford mandelic acid derivatives in excellent yields under ambient CO2 pressure. Both transformations enabled the synthesis of alpha-tertiary and alpha-quaternary carboxylic acid derivatives. In addition, the chirality of (S)-N-tert-butylsulfonyl-alpha-amido stannanes was transferred with up to 90% inversion of configuration at 100 degrees C.

  DOI：

  10.1021/jo202597p

文献信息

• Selective C–F Functionalization of Unactivated Trifluoromethylarenes
  作者：David B. Vogt、Ciaran P. Seath、Hengbin Wang、Nathan T. Jui

  DOI：10.1021/jacs.9b06004

  日期：2019.8.21

  Fluorinated organic molecules are pervasive within the pharmaceutical and agrochemical industries due to the range of structural and physicochemical properties that fluorine imparts. To date, the most abundant methods for the synthesis of the aryl CF2-functionality have relied on the deoxyfluorination of ketones and aldehydes using expensive and poorly atom economical reagents. Here, we report a general

  由于氟赋予的结构和物理化学性质的范围，氟化有机分子在制药和农业化学工业中普遍存在。迄今为止，合成芳基 CF2 官能团的最丰富的方法依赖于使用昂贵且原子经济性差的试剂对酮和醛进行脱氧氟化。在这里，我们报告了通过激活相应的三氟甲基芳烃前体合成芳基-CF2R 和芳基-CF2H 化合物的一般方法。这种策略是通过吸能电子转移事件实现的，该事件提供了对位于催化剂还原电位之外的芳烃自由基阴离子的访问。
• Room Temperature Aryl Trifluoromethylation via Copper-Mediated Oxidative Cross-Coupling
  作者：Todd D. Senecal、Andrew T. Parsons、Stephen L. Buchwald

  DOI：10.1021/jo1023377

  日期：2011.2.18

  A method for the room temperature copper-mediated trifluoromethylation of aryl and heteroaryl boronic acids has been developed. This protocol is amenable to normal benchtop setup and reactions typically require only 1−4 h. Proceeding under mild conditions, the method tolerates a range of functional groups, allowing access to a variety of trifluoromethylarenes.

  已开发出一种用于室温铜介导的芳基和杂芳基硼酸三氟甲基化的方法。该协议适用于正常的台式设置，反应通常只需要 1-4 小时。该方法在温和条件下进行，可耐受一系列官能团，从而可以使用各种三氟甲基芳烃。
• Regio- and Diastereoselective Synthesis of 2-Arylazetidines: Quantum Chemical Explanation of Baldwin’s Rules for the Ring-Formation Reactions of Oxiranes
  作者：Ervin Kovács、Ferenc Faigl、Zoltán Mucsi

  DOI：10.1021/acs.joc.0c01310

  日期：2020.9.4

  A general, scalable two-step regio- and diastereoselective method has been described for the synthesis of versatile alkaloid-type azetidines from simple building blocks with excellent overall yields. In the kinetically controlled reaction, only the formation of the strained four-membered ring can be achieved instead of the thermodynamically favorable five-membered rings under appropriate conditions

  已经描述了一种通用的，可扩展的两步区域和非对映选择性方法，用于从简单的结构单元以优异的总产率合成通用的生物碱型氮杂环丁烷。在动力学控制的反应中，仅在适当的条件下可以形成应变的四元环，而不是热力学上有利的五元环。还证明了显着的官能团耐受性。在本文中，我们通过具有明确溶剂模型的密度泛函理论（DFT）计算，给出了鲍德温规则的新范围，从而证实了所提出的反应机理以及动力学控制在所报道的无过渡金属碳的立体化学结果中的作用–碳键形成反应。
• Suzuki–Miyaura Cross-Coupling Reactions of Potassium Boc-Protected Aminomethyltrifluoroborate with Aryl and Hetaryl Mesylates
  作者：Gary A. Molander、Inji Shin

  DOI：10.1021/ol301221p

  日期：2012.6.15

  Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions were studied with potassium Boc-protected aminomethyltrifluoroborate through C-O activation of various mesylate derivatives to afford the corresponding products in moderate to good yields.
• Pd-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions between Sulfamates and Potassium Boc-Protected Aminomethyltrifluoroborates
  作者：Gary A. Molander、Inji Shin

  DOI：10.1021/ol401021x

  日期：2013.5.17

  Sulfamates were studied as the electrophilic partners in the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction with potassium Boc-protected primary and secondary aminomethyltrifluoroborates. A broad range of substrates was successfully coupled to provide the desired products. Complex molecules containing a new carbon-carbon bond and an aminomethyl moiety could be prepared through this developed method.