tert-butyl 2-(3,5-bis(trifluoromethyl)phenyl)pyrrolidine-1-carboxylate | 1639364-06-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: tert-butyl 2-(3,5-bis(trifluoromethyl)phenyl)pyrrolidine-1-carboxylate
• 英文别名: t-butyl 2-[3,5-bis(trifluoromethyl)phenyl]pyrrolidine-1-carboxylate；N-Boc-2(3,5-bistrifluoromethylphenyl)pyrrolidine；1-(tert-Butoxycarbonyl)-2-[3,5-bis(trifluoromethyl)phenyl]pyrrolidine；tert-butyl 2-[3,5-bis(trifluoromethyl)phenyl]pyrrolidine-1-carboxylate
• CAS: 1639364-06-9
• 化学式: C₁₇H₁₉F₆NO₂
• 分子量: 383.334
• InChiKey: YKEARFAETXFSGJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  tert-butyl 2-(3,5-bis(trifluoromethyl)phenyl)pyrrolidine-1-carboxylate 在 正丁基锂 、 四甲基乙二胺 、 仲丁基锂 作用下， 以 乙醚 、 正己烷 、 环己烷 为溶剂， 反应 22.0h， 生成
  参考文献：
  名称：

  Diastereoselective synthesis of α,α,α′-trisubstituted pyrrolidines and piperidines by directed sequential lithiation/alkylation

  摘要：

  The stereocontrolled synthesis of alpha,alpha,alpha'-trisubstituted pyrrolidines and piperidines has been accomplished through alpha'-lithiation/trapping of the corresponding alpha,alpha-disubstituted Boc-protected azaheterocycle with various electrophiles. The relative configuration of the major diastereomer has the alpha'-substituent trans to the alpha-aryl group in the pyrrolidines but cis to the alpha-aryl group in the piperidines. The diastereoselectivity of the lithiation/alkylation of pyrrolidines is unaffected by TMEDA but decreases in the presence of (-)-sparteine in diethyl ether. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.11.031
• 作为产物：
  描述：

  在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 tert-butyl 2-(3,5-bis(trifluoromethyl)phenyl)pyrrolidine-1-carboxylate
  参考文献：
  名称：

  通过光氧化还原和镍催化的合并对α-氨基酸进行对映选择性脱羧芳基化

  摘要：

  通过光氧化还原和镍催化的协同合并实现了不对称脱羧 Csp(3)-Csp(2) 交叉耦合。这种温和、操作简单的方案将各种天然丰富的 α-氨基酸和容易获得的芳基卤化物转化为高对映体过量的有价值的手性苄胺，从而产生在药理活性剂中发现的基序。

  DOI：

  10.1021/jacs.5b13211

文献信息

• Heterogeneous Titania-Photoredox/Nickel Dual Catalysis: Decarboxylative Cross-Coupling of Carboxylic Acids with Aryl Iodides
  作者：Christopher D. McTiernan、Xavier Leblanc、Juan C. Scaiano

  DOI：10.1021/acscatal.6b03687

  日期：2017.3.3

  The efficient, mild, and semiheterogeneous decarboxylative cross-coupling of a variety alkyl carboxylic acids with aryl iodides has been accomplished through a merger of TiO2 photoredox and nickel cross-coupling chemistries. The protocol is tolerant to a wide range of substituted aryl iodides and alkyl carboxylic acids. Through replacement of the commonly employed Ir transition-metal complexes with

  各种烷基羧酸与芳基碘化物的高效，温和和半均质的脱羧交叉偶联已经通过TiO 2光还原和镍交叉偶联化学的结合来实现。该方案可耐受多种取代的芳基碘化物和烷基羧酸。通过用P25 TiO 2作为光催化剂代替常用的Ir过渡金属配合物，我们表明这些转变可以被异质化，而对这些转变的效率几乎没有影响，同时由于可重复使用性和可回收性而降低了相关成本。 TiO 2光催化剂的廉价性质。
• Effects of Molecular Oxygen, Solvent, and Light on Iridium-Photoredox/Nickel Dual-Catalyzed Cross-Coupling Reactions
  作者：Martins S. Oderinde、Adrian Varela-Alvarez、Brian Aquila、Daniel W. Robbins、Jeffrey W. Johannes

  DOI：10.1021/acs.joc.5b01193

  日期：2015.8.7

  with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.

  为了在铱-光氧化还原和镍双催化的sp 3 -sp 2碳-碳键形成反应中实现可重复性，我们研究了分子氧（O 2），溶剂和光源（CF灯或蓝色LED）的作用）参与各种Ir-光氧化还原介导的转化。当在CF灯辐照下将空气稳定的Ni（II）预催化剂用于DMF中时，发现O 2的存在对于催化剂活化很重要。但是，在同一反应体系中用Ni（COD）2进行催化时，不需要O 2进行催化。认为O 2促进了Ir（II）将Ni（II）预催化剂快速还原为Ni（0）。除了O参照图2，将讨论溶剂和光源对双催化的脱羧交叉偶联反应的影响。这些发现使我们能够开发出更可靠的双催化脱羧交叉偶联方案。
• Merging photoredox with nickel catalysis: Coupling of α-carboxyl sp ³ -carbons with aryl halides
  作者：Zhiwei Zuo、Derek T. Ahneman、Lingling Chu、Jack A. Terrett、Abigail G. Doyle、David W. C. MacMillan

  DOI：10.1126/science.1255525

  日期：2014.7.25

  can be systematically used as coupling partners. By using this photoredox-metal catalysis approach, we have achieved a direct decarboxylative sp3–sp2 cross-coupling of amino acids, as well as α-O– or phenyl-substituted carboxylic acids, with aryl halides. Moreover, this mode of catalysis can be applied to direct cross-coupling of Csp3–H in dimethylaniline with aryl halides via C–H functionalization.

  碳偶联的光明前景 在当代有机化学中，使用交叉偶联催化在不饱和碳（即已经形成双键的碳）之间形成键是很简单的。然而，如果一个或两个起始碳中心饱和（纯单键），该协议就会遇到一些麻烦。特利斯等人。和左等人。独立发现，将第二种光活化催化剂与镍交叉偶联催化剂结合可以实现饱和和不饱和试剂的选择性偶联（参见 Lloyd-Jones 和 Ball 的观点）。他们的方法依赖于从光活化催化剂到饱和碳的单电子转移，从而比传统方案中盛行的双电子机制更有效地增强其反应性。科学，这个问题 p。433 页。第437话 另见第 381 结合两种催化剂，一种是光活化的，可以促进饱和碳和不饱和碳之间的键形成。[另见 Lloyd-Jones 和 Ball 的观点] 在过去的 40 年里，过渡金属催化使芳基和烯烃 (sp2) 碳之间的键形成能够以选择性和可预测的方式形成，具有高官能团耐受性。涉及烷基 (sp3) 碳的偶联已被证明更
• Decarboxylative cross-coupling and applications thereof
  申请人：THE TRUSTEES OF PRINCETON UNIVERSITY

  公开号：US10538509B2

  公开（公告）日：2020-01-21

  Methods described herein enable the production of numerous molecular species through decarboxylative cross-coupling via use of photoredox and transition metal catalysts. A method described herein, in some embodiments, comprises providing a reaction mixture including a photoredox catalyst, a transition metal catalyst, a coupling partner and a substrate having a carboxyl group. The reaction mixture is irradiated with a radiation source resulting in cross-coupling of the substrate and coupling partner via a mechanism including decarboxylation, wherein the coupling partner is selected from the group consisting of a substituted aromatic compound and a substituted aliphatic compound.

  本文所述的方法可通过使用光氧化还原和过渡金属催化剂进行脱羧交叉偶联来生产多种分子物质。在某些实施方案中，本文所述的方法包括提供一种反应混合物，其中包括一种光氧化催化剂、一种过渡金属催化剂、一种偶联剂和一种具有羧基的基质。用辐射源照射反应混合物，通过包括脱羧在内的机理使基质和偶联剂发生交叉偶联，其中偶联剂选自由取代的芳香族化合物和取代的脂肪族化合物组成的组。
• DECARBOXYLATIVE CROSS-COUPLING AND APPLICATIONS THEREOF
  申请人：THE TRUSTEES OF PRINCETON UNIVERSITY

  公开号：US20170022185A1

  公开（公告）日：2017-01-26

  Methods described herein enable the production of numerous molecular species through decarboxylative cross-coupling via use of photoredox and transition metal catalysts. For example, methods described herein enable the production of numerous molecular species through decarboxylative cross-coupling via use of photoredox and transition metal catalysts. A method described herein, in some embodiments, comprises providing a reaction mixture including a photoredox catalyst, a transition metal catalyst, a coupling partner and a substrate having a carboxyl group. The reaction mixture is irradiated with a radiation source resulting in cross-coupling of the substrate and coupling partner via a mechanism including decarboxylation, wherein the coupling partner is selected from the group consisting of a substituted aromatic compound and a substituted aliphatic compound.