tert-butyl 2-(o-tolyl)pyrrolidine-1-carboxylate | 164919-14-6

• 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-(o-tolyl)pyrrolidine-1-carboxylate
• 英文别名: tert-butyl 2-(2-methylphenyl)pyrrolidine-1-carboxylate
• CAS: 164919-14-6
• 化学式: C₁₆H₂₃NO₂
• 分子量: 261.364
• InChiKey: GSFHSMPUPSNMTD-UHFFFAOYSA-N

物化性质

• 沸点：
  362.0±31.0 °C(Predicted)
• 密度：
  1.056±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl 2-(o-tolyl)pyrrolidine-1-carboxylate 在 四甲基乙二胺 、 仲丁基锂 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  Synthetic Applications and Inversion Dynamics of Configurationally Stable 2-Lithio-2-arylpyrrolidines and -piperidines

  摘要：

  In diethyl ether, N-Boc-2-lithio-2-arylpiperidines have been found to be configurationally stable at -80 degrees C, whereas N-Boc-2-lithio-2-arylpyrrolidines are configurationally stable at -60 degrees C. Several tertiary benzylic carbanions derived from enantioenriched 2-aryl heterocycles have been successfully alkylated or acylated with little to no loss of enantiopurity. The scope of the reactions has been explored. The enantiomerization dynamics of N-Boc-2-lithio-2-phenylpyrrolidine and N-Boc-2-lithio-2-phenylpiperidine have been studied in the presence of different solvents and achiral ligands.

  DOI：

  10.1021/ja306276w
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 4-二甲氨基吡啶 、 bis-triphenylphosphine-palladium(II) chloride 、 四甲基乙二胺 、 仲丁基锂 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 42.5h， 生成 tert-butyl 2-(o-tolyl)pyrrolidine-1-carboxylate
  参考文献：
  名称：

  Copper Cyanide-Catalyzed Palladium Coupling of N-tert-Butoxycarbonyl-Protected α-Lithio Amines with Aryl Iodides or Vinyl Iodides

  摘要：

  Treatment of (alpha-aminoalkyl)lithium reagents with aryl iodides in the presence of catalytic amounts of CuCN and PdCl2(PPh3)(2) or [(p-MeOC6H4)(3)P](4)Pd affords 2-aryl substituted amines in modest to good yields. The yields can be improved by use of softer ligands such as AsPh3 and SbPh3 or by use of bis(diphenylphosphino)ferrocene (dppf). Coupled products are obtained with electron-rich aryl iodides (XArI, X = Me, OMe), and the reaction fails with electron-poor aryl iodides (XArI, X = NO2, CO2Li). Treatment of the (alpha-aminoalkyl)lithium reagents with vinyl iodides and Pd(0)/dppf/CuCN afforded the coupling products in low to modest yields.

  DOI：

  10.1021/jo970985b

文献信息

• Benzaldehyde- and Nickel-Catalyzed Photoredox C(sp³)–H Alkylation/Arylation with Amides and Thioethers
  作者：Xiaojia Si、Lumin Zhang、A. Stephen K. Hashmi

  DOI：10.1021/acs.orglett.9b02226

  日期：2019.8.16

  Herein a synergistic combination of a nickel catalyst and benzaldehyde for the utilization of amides and thioethers in C(sp3)–H alkylation and arylation reactions employing simple aryl or alkyl halides is reported. This method provides a simple and cheap strategy for the direct functionalization of amides and thioethers. Readily available starting materials, mild reaction conditions, a good functional-group

  本文报道了镍催化剂和苯甲醛的协同组合，用于利用简单的芳基或烷基卤化物在C（sp 3）-H烷基化和芳基化反应中利用酰胺和硫醚。该方法为酰胺和硫醚的直接官能化提供了一种简单而廉价的策略。易于获得的起始原料，温和的反应条件，良好的官能团耐受性和广泛的底物范围使该方法对于药物和合成化学具有吸引力且实用。
• Native functionality in triple catalytic cross-coupling: sp ³ C–H bonds as latent nucleophiles
  作者：Megan H. Shaw、Valerie W. Shurtleff、Jack A. Terrett、James D. Cuthbertson、David W. C. MacMillan

  DOI：10.1126/science.aaf6635

  日期：2016.6.10

  carbon centers adjacent to nitrogen or oxygen. The use of sp3 C–H bonds—which are ubiquitous in organic molecules—as latent nucleophile equivalents for transition metal–catalyzed cross-coupling reactions has the potential to substantially streamline synthetic efforts in organic chemistry while bypassing substrate activation steps. Through the combination of photoredox-mediated hydrogen atom transfer (HAT)

  从 HAT 到 CC 键的形成 铱和镍已经是锻造碳-碳键的成熟团队。铱从一个简单的发光二极管收集蓝光，并通过镍协调耦合。肖等人。现在为团队添加第三名球员，即氢原子转移 (HAT) 催化剂（参见 Fruit 的观点）。这三种催化剂一起可以将溴或氯芳基环直接连接到与氮或氧相邻的 CH 位点，无需事先修饰。该反应对广泛的底物具有高度选择性。科学，这个问题 p。1304; 另见第。1277 三种催化剂将芳环附加到与氮或氧相邻的各种碳中心。使用 sp3 C-H 键（在有机分子中普遍存在）作为过渡金属催化交叉偶联反应的潜在亲核试剂等价物，有可能大大简化有机化学中的合成工作，同时绕过底物活化步骤。通过光氧化还原介导的氢原子转移 (HAT) 和镍催化的结合，我们开发了一种高选择性和通用的 C-H 芳基化方案，可激活各种 C-H 键作为交叉偶联的天然功能手柄。这种温和的方法利用可调节的 HAT 催化剂，该催
• Mechanistic Insight into the Photoredox-Nickel-HAT Triple Catalyzed Arylation and Alkylation of α-Amino C_sp3–H Bonds
  作者：Bholanath Maity、Chen Zhu、Huifeng Yue、Long Huang、Moussab Harb、Yury Minenkov、Magnus Rueping、Luigi Cavallo

  DOI：10.1021/jacs.0c05010

  日期：2020.10.7

  indicating that both reductive and oxidative quenching catalytic cycles can be operative, although the reductive cycle is favored. Our analysis of the HAT cycle indicated that activation of a α-amino Csp3‒H bond of the substrate is facile and selective relative to activation of a β-amino Csp3‒H bond. Finally, our analysis of the nickel cycle indicated that both arylation and alkylation of α-amino Csp3-H

  我们在此报告了对由 MacMillan 及其同事开发的光氧化还原-镍-HAT（HAT：氢原子转移）催化的 α-氨基 Csp3-H 键的芳基化和烷基化机制的综合计算分析。测试了三个催化循环的不同替代方案，以明确确定操作反应机制。我们的分析表明，在可见光照射下，IrIII 光氧化还原催化剂可以分别被 HAT 和镍催化剂还原或氧化，这表明还原和氧化猝灭催化循环都可以进行，尽管还原循环是有利的。我们对 HAT 循环的分析表明，相对于 β-氨基 Csp3-H 键的激活，底物的 α-氨基 Csp3-H 键的激活是容易和选择性的。最后，
• Nickel‐Catalyzed Thermal Redox Functionalization of C(sp ³ )−H Bonds with Carbon Electrophiles**
  作者：Yuxin Gong、Lei Su、Zhaodong Zhu、Yang Ye、Hegui Gong

  DOI：10.1002/anie.202201662

  日期：2022.5.23

  Under thermal conditions, nickel-catalyzed C(sp3)−H redox functionalization with carbon electrophiles has been advanced to forge value-added C(sp3)−C bonds in good to excellent efficiency. This method emphasizes the use of external Zn as reductant and di-tert-butyl peroxide as an oxidant and shows remarkable compatibility with Ni-catalysis.

  在热条件下，镍催化的碳亲电试剂的 C(sp 3 )-H 氧化还原功能化已被推进，以形成具有良好至优异效率的增值 C(sp 3 )-C 键。该方法强调使用外部 Zn 作为还原剂和二叔丁基过氧化物作为氧化剂，并显示出与 Ni 催化的显着相容性。
• Copper cyanide catalyzed palladium coupling of α-lithio amines and aryl iodides
  作者：R.Karl Dieter、ShengJian Li

  DOI：10.1016/0040-4039(95)00577-y

  日期：1995.5

  Treatment of alpha-aminoalkyllithium reagents with aryl iodides in the presence of catalytic amounts of CuCN and PdCl2(PPh(3))(2) or [(p-MeOC(6)H(4))(3)P]Pd-4 affords 2-aryl substituted amines in modest to good yields. Coupled products are obtained with electron rich aryl iodides and the reaction fails with electron poor aryl halides.