N-(furan-2-ylmethyl)-3-methoxyaniline | 95124-24-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: N-(furan-2-ylmethyl)-3-methoxyaniline
• CAS: 95124-24-6
• 化学式: C₁₂H₁₃NO₂
• 分子量: 203.241
• InChiKey: YAEDHNFGHUNKBQ-UHFFFAOYSA-N

物化性质

• 沸点：
  162-163 °C(Press: 5 Torr)
• 密度：
  1.152±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  34.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(furan-2-ylmethyl)-3-methoxyaniline 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 72.0h， 生成 3-(3-Methoxy-phenyl)-10-oxa-3-aza-tricyclo[5.2.1.0^1,5]dec-8-ene; compound with picric acid
  参考文献：
  名称：

  呋喃系列研究。22.N-芳基糠基和5-甲基糠基胺及其N-烯丙基衍生物

  摘要：

  DOI：

  10.1021/je00040a034
• 作为产物：
  描述：

  1-(呋喃-2-基)-N-(3-甲氧基苯基)甲亚胺 在 甲醇 、 碘 、 magnesium 作用下， 以80%的产率得到N-(furan-2-ylmethyl)-3-methoxyaniline
  参考文献：
  名称：

  呋喃系列研究。22.N-芳基糠基和5-甲基糠基胺及其N-烯丙基衍生物

  摘要：

  DOI：

  10.1021/je00040a034

文献信息

• Controlling First-Row Catalysts: Amination of Aryl and Heteroaryl Chlorides and Bromides with Primary Aliphatic Amines Catalyzed by a BINAP-Ligated Single-Component Ni(0) Complex
  作者：Shaozhong Ge、Rebecca A. Green、John F. Hartwig

  DOI：10.1021/ja411911s

  日期：2014.1.29

  Mechanistic studies support the catalytic cycle involving a Ni(0)/Ni(II) couple for this nickel-catalyzed amination and are inconsistent with a Ni(I) halide intermediate. Monitoring the reaction mixture by 31P NMR spectroscopy identified (BINAP)Ni(η2-NC-Ph) as the resting state of the catalyst in the amination of both aryl chlorides and bromides. Kinetic studies showed that the amination of aryl chlorides

  在催化循环的两电子步骤期间，第一排金属配合物经常经历不希望的单电子氧化还原过程。我们报告了由定义明确的单组分镍前体 (BINAP)Ni(η2-NC-Ph) (BINAP = 2,2'-bis(biphenylphosphino)-1) 催化的芳基氯化物和溴化物与脂肪族伯胺的胺化,1'-联萘)，最大限度地减少 Ni(I) 物质和 (BINAP)2Ni 的形成。该反应的范围包括电子变化的芳基氯化物和含氮杂芳基氯化物，包括吡啶、喹啉和异喹啉衍生物。机理研究支持涉及用于这种镍催化胺化的 Ni(0)/Ni(II) 对的催化循环，并且与 Ni(I) 卤化物中间体不一致。通过 31P NMR 光谱监测反应混合物，确定 (BINAP)Ni(η2-NC-Ph) 是芳基氯化物和溴化物胺化中催化剂的静止状态。动力学研究表明，芳基氯化物和溴化物的胺化在催化剂和芳基卤化物中均为一级，在碱和胺中为零级。代表性芳基氯在
• Application of Diazaphospholidine/Diazaphospholene-Based Bisphosphines in Room-Temperature Nickel-Catalyzed C(sp²)–N Cross-Couplings of Primary Alkylamines with (Hetero)aryl Chlorides and Bromides
  作者：Alexandre V. Gatien、Christopher M. Lavoie、Raymond N. Bennett、Michael J. Ferguson、Robert McDonald、Erin R. Johnson、Alexander W. H. Speed、Mark Stradiotto

  DOI：10.1021/acscatal.8b01005

  日期：2018.6.1

  donor fragment paired with an adjacent PR2 donor group (R = alkyl, aryl), whereby the incorporation of phosphorus into either a saturated or unsaturated heterocyclic ring serves as a means of modulating the donicity of the NHP fragment. Screening of these ancillary ligands in representative nickel-catalyzed C(sp2)–N cross-coupling test reactions allowed for the identification of one variant, featuring

  我们在本文中报道了邻苯撑桥联双膦辅助配体家族的合成和催化应用，该配体具有庞大的N-杂环膦（NHP）供体片段与相邻的PR 2供体基团（R =烷基，芳基）配对，从而将磷结合到饱和或不饱和杂环中可作为调节NHP片段电荷的手段。在代表性镍催化的C（sp 2中筛选这些辅助配体）–N交叉偶联测试反应可鉴定一种具有饱和NHP结构和相邻的二苯基膦基供体基团（即NHP-DalPhos）的变体，在涉及伯烷基胺的反应中特别有效。值得注意的是，在室温下应用衍生的预催化剂（NHP-DalPhos）NiCl（邻甲苯基）（C1）可以使结构多样的伯烷基胺与（杂）芳基氯化物或溴化物进行典型的挑战性单芳基化。还描述了我们采用PAd-DalPhos或NHP-DalPhos对镍催化的伯烷基胺C（sp 2）-N交叉偶联进行比较密度泛函理论计算分析的结果。
• A Comparative Reactivity Survey of Some Prominent Bisphosphine Nickel(II) Precatalysts in C–N Cross-Coupling
  作者：Jillian S. K. Clark、Christopher M. Lavoie、Preston M. MacQueen、Michael J. Ferguson、Mark Stradiotto

  DOI：10.1021/acs.organomet.6b00650

  日期：2016.9.26

  The synthesis and characterization of the new air-stable precatalyst (L1)Ni(o-tol)Cl (Cl; where L1 = JosiPhos CyPF-Cy) is reported, along with the results of a comparative reactivity survey involving Cl and analogous PAd-DalPhos- and DPPF-containing precatalysts (C2 and C3, respectively) in representative nickel-catalyzed C(sp(2))-N cross-coupling reactions. Precatalyst C1 was found to be competitive with, and in some cases complementary to, C2 in the monoarylation of ammonia and primary alkylamines with (hetero)aryl chlorides, including in otherwise challenging room temperature transformations. (Pseudo)halide comparison studies involving the cross-coupling of furfurylamine at room temperature revealed that in contrast to C2 precatalyst Cl performs less effectively with aryl bromides. Whereas C3 was found to be ineffective for such transformations, this DPPF-derived precatalyst proved superior to C1 and C2 in reactions involving the secondary dialkylamine test substrate morpholine.
• Evaluating 1,1′-Bis(phosphino)ferrocene Ancillary Ligand Variants in the Nickel-Catalyzed C–N Cross-Coupling of (Hetero)aryl Chlorides
  作者：Jillian S. K. Clark、Christopher N. Voth、Michael J. Ferguson、Mark Stradiotto

  DOI：10.1021/acs.organomet.6b00885

  日期：2017.2.13

  Previous reports in the literature have established the utility of 1,1'-bis(diphenylphosphino)ferrocene (DPPF, L-Ph) in the nickel-catalyzed cross-coupling of (hetero)aryl electrophiles with primary or secondary amines. In an effort to evaluate the effect of varying the PR2-donor groups On catalytic performance in such transformations, a series of 10 structurally varied 1,1'-bis(bis(alkyl/aryl)phosphino)ferrocene ancillary ligands (L-X) were systematically examined in selected competitive test cross couplings of (hetero)aryl halides with furfurylamine, morpholine, and indole employing Ni(COD)(2)/L-X catalyst mixtures. In addition to the excellent performance observed for the parent ligand LPh in a number of the test transformations explored, selected dialkylphosphino (e.g., DiPPF, L-iPr) and meta-disubstituted diarylphosphino variants of L-Ph also proved highly effective. In particular, the electron-deficient ligand variant L-CF3 featuring 3,5-bis(trifluoromethyl)phenyl groups on phosphorus was found to exhibit superior catalytic performance relative to L-Ph in most of the test transformations involving the N-arylation of indole. Our efforts to prepare Ni(II) precatalysts of the type (L-X)Ni(o-tolyl)Cl) in analogy with known (L-Ph)Ni(o-tolyl)Cl, by employing several literature methods met with mixed results. Whereas ((LNi)-Ni-iPr(o-tolyl)Cl was prepared straightforwardly and was crystallographically characterized, the use of L-CF3 or ligands featuring tert-butyl (L-tBu, o-tolyl (Lo-tol), or 4-methoxy-3,5dirnethylphenyl (L-OMe) groups on phosphorus under similar conditions resulted in poor conversion to product and/or the formation of poorly soluble materials, highlighting the limitations of this commonly used precatalyst design.
• Indium trifluoromethanesulfonate (In(OTf)3). A novel reusable catalyst for intramolecular Diels–Alder reactions
  作者：Dipak Prajapati、Dhrubojyoti D Laskar、Jagir S Sandhu

  DOI：10.1016/s0040-4039(00)01513-6

  日期：2000.10

  Indium trifluoromethanesulfonate (In(OTf)(3)) is found to be an effective catalyst for intramolecular Diels-Alder reactions of furans. This novel catalyst, soluble in both aqueous and organic media, is easily recovered from the aqueous layer after the reaction is completed. (C) 2000 Elsevier Science Ltd. All rights reserved.