N-(2-(diphenylphosphaneyl)benzyl)-1-(pyridin-2-yl)methanamine | 958463-19-9

• 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: N-(2-(diphenylphosphaneyl)benzyl)-1-(pyridin-2-yl)methanamine
• 英文别名: 1-(2-diphenylphosphanylphenyl)-N-(pyridin-2-ylmethyl)methanamine
• CAS: 958463-19-9
• 化学式: C₂₅H₂₃N₂P
• 分子量: 382.445
• InChiKey: HIKIDERWVMBVRQ-UHFFFAOYSA-N

物化性质

• 沸点：
  514.5±40.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  24.9
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tris(triphenylphosphine)ruthenium(II) chloride 、 N-(2-(diphenylphosphaneyl)benzyl)-1-(pyridin-2-yl)methanamine 以 二氯甲烷 为溶剂， 以82%的产率得到trans-[RuCl2(PPh3)Ph2P(o,o'-C6H4CH2NHCH2C5H4N)]
  参考文献：
  名称：

  [RuCl₂(PPh₃)(PNN‘)] Complexes as Efficient Catalysts in Transfer Hydrogenation of Ketones

  摘要：

  Ruthenium complexes of the general formula [RuCl2(PPh3)(PNN')] have been obtained from tridentate PNN' ligands containing phosphine (P), amine or imine (N), and pyridyl donor groups (N'). The imino ligand Ph2P(o,o'-C6H4CH=NCH2C5H4N) (a) has been synthesized from Ph2P(2-C6H4CHO) and 2-(aminomethyl)pyridine, whereas amino Ph2P(o,o'-C6H4CH2NHCH2C5H4N) (b) is prepared by the reduction of a with NaBH4. The complexes trans-[RuCl2(PPh3)(PNN')] [PNN' = b, (1); a, (2)] containing a five-membered NN' cycle have been isolated in high yield by the reaction of RuCl2(PPh3)(3) with b and a, respectively. By the same route and using the ligand Ph2P(o,o'-C6H4CH=NCH2CH2C5H4N)] (c), the complex cis-[RuCl2(PPh3)(c)] (3) was isolated, and it displays a different stereochemistry as a result of the different size of the tridentate ligand. For the amino derivative 1, an X-ray diffraction experiment was carried out. Treatment of [RuHCl(PPh3)(3)] with the ligands a or b leads to the monohydride complexes trans-[RuHCl(PPh3)(PNN')] [PNN' = b, (4); a, (5)]. Complexes 1-5 have been proven to catalyze the transfer hydrogenation of linear, cyclic, and aromatic ketones to secondary alcohols in 2-propanol at reflux and in the presence of (CH3)(2)CHONa with a very high rate (TOF values up to 250 000 h(-1)). The trans derivatives 1 and 2 containing the amino and imino functions catalyze the reduction of acetophenone with the same activity (TOF = 190 000 and 185 000 h(-1), respectively), suggesting that the C=N group is reduced during catalysis. A lower activity has been observed for complexes 3-5.

  DOI：

  10.1021/om700647k
• 作为产物：
  描述：

  2-二苯基膦苯甲醛 在 sodium tetrahydroborate 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 18.0h， 生成 N-(2-(diphenylphosphaneyl)benzyl)-1-(pyridin-2-yl)methanamine
  参考文献：
  名称：

  金（I）配合物中的异位P，N配体：合成，结构和细胞毒性

  摘要：

  合成了新的异位，双齿和多齿亚氨基和氨基膦配体，并与[AuCl（THT）]（THT =四氢噻吩）络合。X射线晶体学证实三种产品中均形成了席夫碱，成功地将亚氨基还原为sp 3-在几种情况下使胺杂化，并确认形成了四个Au配合物的单金（I）亚氨基和氨基膦配合物。在癌细胞和非癌细胞系中的细胞毒性研究表明，配体与金（I）配合后，细胞毒性显着增加。这些发现得到了美国国立卫生研究院发育治疗计划60种细胞株指纹屏筛选两种有希望的化合物的结果的支持。这些配体和金（I）配合物的某些细胞毒性是由于细胞凋亡的诱导。配体和金（I）配合物表现出对特定细胞系的选择性毒性，而Jurkat T细胞对这些化合物的细胞毒性作用更为敏感，而与癌细胞系相比，非癌细胞系KMST6具有更强的抗性。NIH DTP 60细胞系指纹筛选的结果支持在Gold（I）络合后观察到的细胞毒性增强。在本研究筛选的所有细胞系中，一种金（I）配合物在50μ

  DOI：

  10.1016/j.jinorgbio.2015.01.014
• 作为试剂：
  描述：

  4-甲氧基苯甲酸甲酯 在 tris(triphenylphosphine)ruthenium(II) chloride 、 N-(2-(diphenylphosphaneyl)benzyl)-1-(pyridin-2-yl)methanamine 、 potassium methanolate 、 氢气 作用下， 以 甲苯 为溶剂， 130.0 ℃ 、8.0 MPa 条件下， 生成 4-甲氧基苄醇
  参考文献：
  名称：

  HYDROGENATION OF ESTERS TO ALCOHOLS IN THE PRESENCE OF A RU-PNN COMPLEX

  摘要：

  Method for hydrogenating an ester with molecular hydrogen to the corresponding alcohols in the presence of a ruthenium complex (I), wherein said complex comprises a tridentate ligand L of the general formula (II) n and m are each independently 0 or 1, and the solid-dashed double lines represent a single or double bond, with the proviso that in the case of n=1 both solid-dashed double lines represent a single bond and m is 1, and in the case of n=0 one solid-dashed double line represents a single bond and the other solid-dashed double line represents a double bond, wherein in the case of a double bond on the side facing the phenyl ring m=1, in the case of a double bond on the side facing the pyridyl ring m=0, or both solid-dashed double lines represent a single bond and m is 1.

  公开号：

  US20220380279A1

文献信息

• [EN] MONOCARBONYL RUTHENIUM AND OSMIUM CATALYSTS<br/>[FR] CATALYSEURS MONOCARBONYLE DE RUTHÉNIUM ET D'OSMIUM
  申请人：UNIVERSITA' DEGLI STUDI DI UDINE

  公开号：WO2017134618A1

  公开（公告）日：2017-08-10

  The invention relates to monocarbonyl complexes of ruthenium and osmium with bi- and tridentate nitrogen and phosphine ligands. The invention relates to methods for preparing these complexes and the use of these complexes, isolated or prepared in situ, as catalysts for reduction reactions of ketones and aldehydes both via transfer hydrogenation or hydrogenation with hydrogen.

  这项发明涉及具有双齿和三齿氮磷配体的钌和锇的单羰基配合物。该发明涉及制备这些配合物的方法以及将这些配合物（无论是分离的还是原位制备的）用作酮和醛的还原反应的催化剂，可以通过氢转移加氢或氢气加氢进行。
• Hydrogenation of Esters by Manganese Catalysts
  作者：Xiao‐Gen Li、Fu Li、Yue Xu、Li‐Jun Xiao、Jian‐Hua Xie、Qi‐Lin Zhou

  DOI：10.1002/adsc.202101376

  日期：2022.2.15

  The hydrogenation of esters catalyzed by a manganese complex of phosphine-aminopyridine ligand was developed. Using this protocol, a variety of (hetero)aromatic and aliphatic carboxylates including biomass-derived esters and lactones were hydrogenated to primary alcohols with 63–98% yields. The manganese catalyst was found to be active for the hydrogenation of methyl benzoate, providing benzyl alcohol

  开发了膦-氨基吡啶配体锰络合物催化酯的氢化反应。使用该协议，各种（杂）芳香族和脂肪族羧酸盐（包括生物质衍生的酯和内酯）被氢化成伯醇，产率为 63-98%。发现锰催化剂对苯甲酸甲酯的氢化具有活性，可提供高达 45,000 的周转数 (TON) 的苯甲醇。对催化剂中间体的研究表明，酰胺锰络合物是该反应的活性催化剂。
• Manganese‐Catalyzed Hydrogenation of Sclareolide to Ambradiol
  作者：Viktoriia Zubar、Niels Lichtenberger、Mathias Schelwies、Thomas Oeser、A. Stephen K. Hashmi、Thomas Schaub

  DOI：10.1002/cctc.202101443

  日期：2022.1.10

  Pincer complexes: A simple and practical approach for the hydrogenation of (+)-Sclareolide to (−)-Ambradiol. The applied manganese catalyst can be prepared in two steps starting from commercially available starting materials. The procedure can be applied for a number of other esters highlighting the versatility of the developed protocol.

  钳形配合物：一种简单实用的方法，用于将 (+)-香紫苏内酯氢化为 (-)-Ambradiol。应用的锰催化剂可以从可商购的起始材料开始分两步制备。该程序可应用于许多其他酯类，突出了开发协议的多功能性。
• Zinc and cobalt complexes based on tripodal ligands: synthesis, structure and reactivity toward lactide
  作者：Mathieu J.-L. Tschan、Jia Guo、Sumesh K. Raman、Emilie Brulé、Thierry Roisnel、Marie-Noelle Rager、Rémi Legay、Guillaume Durieux、Baptiste Rigaud、Christophe M. Thomas

  DOI：10.1039/c3dt52629a

  日期：——

  The coordination chemistry of a series of pro-ligands ([L1]–[L6]) with cobalt and zinc derivatives has been studied. All complexes have been characterized by multinuclear NMR, elemental analysis, and by single-crystal X-ray diffraction studies. Polymerization of rac-lactide takes place at 130 °C in the presence of cobalt and zinc complexes to yield polymers under solvent free conditions with controlled molecular masses and narrow polydispersities.

  一系列前配体（[L1]–[L6]）与钴和锌衍生物的配位化学已被研究。所有的配合物都通过多核核磁共振、元素分析以及单晶X射线衍射研究进行了表征。在130°C下，在钴和锌配合物的存在下，rac-乳酸内酯发生聚合反应，在无溶剂条件下生成具有可控分子量和窄分布宽度的聚合物。
• Iron‐Catalyzed Deoxynitrogenation of Carboxylic Acids with Cyanamides to Access Nitriles
  作者：Mengsheng Li、Jing Zhang

  DOI：10.1002/chem.202300217

  日期：——

  An iron-catalyzed deoxynitrogenation strategy to convert carboxylic acids into nitriles is reported. This method utilizes a cyanamide as the recyclable nitrogen donor and deoxygenating reagent and features an easy-to-setup without inert gas protection. The synthetic value of this method is highlighted by the broad substrate scope and application in late-stage modification of pharmaceuticals and scaleup

  报道了一种铁催化的脱氧氮化策略，可将羧酸转化为腈。该方法使用氨基氰作为可回收的氮供体和脱氧剂，具有易于设置且无需惰性气体保护的特点。该方法的综合价值体现在广泛的底物范围和药物后期修饰以及放大反应和衍生化中的应用。