chloro{[2-aminoethyl](4-toluenesulfonyl)amido}(p-cymene)ruthenium(II) | 208988-63-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: chloro{[2-aminoethyl](4-toluenesulfonyl)amido}(p-cymene)ruthenium(II)
• 英文别名: [(η⁶-para-cymene)Ru(N-(2-aminoethyl)-4-toluenesulfonamide(1-))Cl]；2-Aminoethyl-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene
• CAS: 208988-63-0
• 化学式: C₁₉H₂₇ClN₂O₂RuS
• 分子量: 484.025
• InChiKey: IEUUIKMNSWHFGZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  69.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  chloro{[2-aminoethyl](4-toluenesulfonyl)amido}(p-cymene)ruthenium(II) 、 重水 生成 [(η⁶-para-cymene)Ru(N-(2-aminoethyl)-4-toluenesulfonamide(1-))(D₂O)](1+)
  参考文献：
  名称：

  Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺

  摘要：

  A series of neutral Ru-II half-sandwich complexes of the type [(eta(6)-arene)Ru(N,N')Cl] where the arene is para-cymene (p-cym), hexamethylbenzene (hmb), biphenyl (bip), or benzene (bn) and N,N' is N-(2-aminoethyl) -4-(trifluoromethyl)benzenesulfonamide (TfEn), N-(2-aminoethyl)-4-toluenesulfonamide (TsEn), or N-(2-aminoethyl)-methylenesulfonamide (MsEn) were synthesized and characterized. X-ray crystal structures of [(p-cym)Ru(MsEn)Cl] (1), [(hmb)Ru(TsEn)Cl] (5), [(hmb)Ru(TfEn)Cl] (6), [(bip)Ru(MsEn)Cl] (7), and [(bip)Ru(TsEn)Cl] (8) have been determined. The complexes can regioselectively catalyze the transfer hydrogenation of NAD(+) to give 1,4-NADH in the presence of formate. The turnover frequencies (TOF) when the arene is varied decrease in the order bn > bip > p-cym > hmb for complexes with the same N,N' chelating ligand. The TOF decreased with variation in the N,N' chelating ligand in the order TfEn > TsEn > MsEn for a given arene. [(bn)Ru(TfEn)Cl] (12) was the most active, with a TOP of 10.4 h(-1). The effects of NAD(+) and formate concentration on the reaction rates were determined for [(p-cym)Ru(TsEn)Cl] (2). Isotope studies implicated the formation of [(arene)Ru(N,N')(H)] as the rate-limiting step. The coordination of formate and subsequent CO2 elimination to generate the hydride were modeled computationally by density functional theory (DFT). CO2 elimination occurs via a two-step process with the coordinated formate first twisting to present its hydrogen toward the metal center. The computed barriers for CO2 release for arene = benzene follow the order MsEn > TsEn > TfEn, and for the Ms En system the barrier followed bn < hmb, both consistent with the observed rates. The effect of methanol on transfer hydrogenation rates in aqueous solution was investigated. A study of pH dependence of the reaction in D2O gave the optimum pH* as 7.2 with a TOF of 1.58 h(-1) for 2. The series of compounds reported here show an improvement in the catalytic activity by an order of magnitude compared to the ethylenediamine analogues.

  DOI：

  10.1021/om3006307
• 作为产物：
  描述：

  [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 N-甲苯磺酰基乙二胺 在 三乙胺 作用下， 以 异丙醇 为溶剂， 以66%的产率得到chloro{[2-aminoethyl](4-toluenesulfonyl)amido}(p-cymene)ruthenium(II)
  参考文献：
  名称：

  荧光和生物相容性钌配位的寡聚（对亚苯基亚乙烯基）纳米催化剂，用于在活细胞的线粒体中转移加氢。

  摘要：

  设计用于活细胞内部具有良好性能的内源性生物分子原位转化的金属催化剂是一项挑战。在这里，我们报告了一种多功能金属催化剂，钌配位的低聚对苯乙炔（OPV-Ru），用于烟酰胺腺嘌呤二核苷酸（NAD +）转移加氢至其还原形式（NADH）的细胞内催化。由于具有两亲特性，OPV-Ru在水中具有良好的自组装能力，可通过疏水相互作用和π-π堆积形成纳米颗粒，并且纳米颗粒表面上的许多正电荷表现出与带负电的底物分子的强静电相互作用，与分散的催化中心分子相比，产生了一个局部微环境以提高催化效率（TOF值提高了约15倍）。OPV-Ru可以选择性地聚集在活细胞的线粒体中。得益于其固有的荧光，可以在荧光显微镜下观察细胞中OPV-Ru的动态分布和摄取行为。这项工作代表了执行多功能有机金属配合物以优异的性能，包括荧光成像能力，特定的线粒体靶向，良好的化学选择性和高催化效率，能够在活细胞的特定亚细胞区隔中催化天然氢化转化的首

  DOI：

  10.1002/chem.201905448
• 作为试剂：
  描述：

  3,7-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal 在 chloro{[2-aminoethyl](4-toluenesulfonyl)amido}(p-cymene)ruthenium(II) 、 sodium formate 、 异丙醇 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以99.6%的产率得到3,7-dimethyl-9-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6,8-nontetraen-1-ol
  参考文献：
  名称：

  [EN] SELECTIVE TRANSFER HYDROGENATION OF RETINAL
  [FR] HYDROGÉNATION PAR TRANSFERT SÉLECTIVE DE RÉTINAL

  摘要：

  本发明涉及将视黄醛选择性转化为视黄醇的转移氢化。

  公开号：

  WO2015004117A1

文献信息

• [EN] SELECTIVE TRANSFER HYDROGENATION OF CITRAL OR ETHYL CITRAL<br/>[FR] HYDROGÉNATION SÉLECTIVE PAR TRANSFERT DE CITRAL OU ÉTHYLE CITRAL
  申请人：DSM IP ASSETS BV

  公开号：WO2015004116A1

  公开（公告）日：2015-01-15

  The present invention relates to a selective transfer hydrogenation of citral to geraniol/nerol and ethyl citral to ethyl geraniol/ethyl nerol.

  本发明涉及将柠檬醛选择性转移加氢成为香叶醇/香叶醇和柠檬醛乙酸乙酯转移加氢成为乙基香叶醇/乙基香叶醇的方法。
• [EN] SELECTIVE TRANSFER HYDROGENATION OF CITRAL OR ETHYL CITRAL<br/>[FR] HYDROGÉNATION PAR TRANSFERT SÉLECTIVE DU CITRAL OU DU CITRAL D'ÉTHYLE
  申请人：DSM IP ASSETS BV

  公开号：WO2015004088A1

  公开（公告）日：2015-01-15

  The present invention relates to a selective transfer hydrogenation of citral to geraniol/nerol and ethyl citral to ethyl geraniol/ethyl nerol.

  本发明涉及柠檬醛选择性转移加氢为香叶醇/香叶醇和柠檬醛乙酯转移加氢为乙基香叶醇/乙基香叶醇的方法。
• Fluorescent and Biocompatible Ruthenium‐Coordinated Oligo( <i>p‐</i> phenylenevinylene) Nanocatalysts for Transfer Hydrogenation in the Mitochondria of Living Cells
  作者：Nan Dai、Hao Zhao、Ruilian Qi、Yanyan Chen、Fengting Lv、Libing Liu、Shu Wang

  DOI：10.1002/chem.201905448

  日期：2020.4.6

  characteristic, OPV-Ru possesses good self-assembly capability in water to form nanoparticles through hydrophobic interaction and π-π stacking, and numerous positive charges on the surface of nanoparticles displayed a strong electrostatic interaction with negatively charged substrate molecules, creating a local microenvironment for enhancing the catalysis efficiency in comparison to dispersed catalytic center

  设计用于活细胞内部具有良好性能的内源性生物分子原位转化的金属催化剂是一项挑战。在这里，我们报告了一种多功能金属催化剂，钌配位的低聚对苯乙炔（OPV-Ru），用于烟酰胺腺嘌呤二核苷酸（NAD +）转移加氢至其还原形式（NADH）的细胞内催化。由于具有两亲特性，OPV-Ru在水中具有良好的自组装能力，可通过疏水相互作用和π-π堆积形成纳米颗粒，并且纳米颗粒表面上的许多正电荷表现出与带负电的底物分子的强静电相互作用，与分散的催化中心分子相比，产生了一个局部微环境以提高催化效率（TOF值提高了约15倍）。OPV-Ru可以选择性地聚集在活细胞的线粒体中。得益于其固有的荧光，可以在荧光显微镜下观察细胞中OPV-Ru的动态分布和摄取行为。这项工作代表了执行多功能有机金属配合物以优异的性能，包括荧光成像能力，特定的线粒体靶向，良好的化学选择性和高催化效率，能够在活细胞的特定亚细胞区隔中催化天然氢化转化的首
• [EN] SELECTIVE TRANSFER HYDROGENATION OF RETINAL<br/>[FR] HYDROGÉNATION PAR TRANSFERT SÉLECTIVE DE RÉTINAL
  申请人：DSM IP ASSETS BV

  公开号：WO2015004117A1

  公开（公告）日：2015-01-15

  The present invention relates to a selective transfer hydrogenation of retinal to retinol.

  本发明涉及将视黄醛选择性转化为视黄醇的转移氢化。
• Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺
  作者：Joan J. Soldevila-Barreda、Pieter C. A. Bruijnincx、Abraha Habtemariam、Guy J. Clarkson、Robert J. Deeth、Peter J. Sadler

  DOI：10.1021/om3006307

  日期：2012.8.27

  A series of neutral Ru-II half-sandwich complexes of the type [(eta(6)-arene)Ru(N,N')Cl] where the arene is para-cymene (p-cym), hexamethylbenzene (hmb), biphenyl (bip), or benzene (bn) and N,N' is N-(2-aminoethyl) -4-(trifluoromethyl)benzenesulfonamide (TfEn), N-(2-aminoethyl)-4-toluenesulfonamide (TsEn), or N-(2-aminoethyl)-methylenesulfonamide (MsEn) were synthesized and characterized. X-ray crystal structures of [(p-cym)Ru(MsEn)Cl] (1), [(hmb)Ru(TsEn)Cl] (5), [(hmb)Ru(TfEn)Cl] (6), [(bip)Ru(MsEn)Cl] (7), and [(bip)Ru(TsEn)Cl] (8) have been determined. The complexes can regioselectively catalyze the transfer hydrogenation of NAD(+) to give 1,4-NADH in the presence of formate. The turnover frequencies (TOF) when the arene is varied decrease in the order bn > bip > p-cym > hmb for complexes with the same N,N' chelating ligand. The TOF decreased with variation in the N,N' chelating ligand in the order TfEn > TsEn > MsEn for a given arene. [(bn)Ru(TfEn)Cl] (12) was the most active, with a TOP of 10.4 h(-1). The effects of NAD(+) and formate concentration on the reaction rates were determined for [(p-cym)Ru(TsEn)Cl] (2). Isotope studies implicated the formation of [(arene)Ru(N,N')(H)] as the rate-limiting step. The coordination of formate and subsequent CO2 elimination to generate the hydride were modeled computationally by density functional theory (DFT). CO2 elimination occurs via a two-step process with the coordinated formate first twisting to present its hydrogen toward the metal center. The computed barriers for CO2 release for arene = benzene follow the order MsEn > TsEn > TfEn, and for the Ms En system the barrier followed bn < hmb, both consistent with the observed rates. The effect of methanol on transfer hydrogenation rates in aqueous solution was investigated. A study of pH dependence of the reaction in D2O gave the optimum pH* as 7.2 with a TOF of 1.58 h(-1) for 2. The series of compounds reported here show an improvement in the catalytic activity by an order of magnitude compared to the ethylenediamine analogues.