Carbohydrate-functionalized N-heterocyclic carbene Ru(ii) complexes: synthesis, characterization and catalytic transfer hydrogenation activity

被引:22
作者
Byrne, Joseph P. [1 ]
Musembi, Pauline [1 ]
Albrecht, Martin [1 ]
机构
[1] Univ Bern, Dept Chem & Biochem, Freiestr 3, CH-3012 Bern, Switzerland
基金
欧洲研究理事会;
关键词
ASYMMETRIC TRANSFER HYDROGENATION; BASE-FREE ALCOHOL; CLICK CHEMISTRY; RUTHENIUM COMPLEXES; LIGANDS SYNTHESIS; C-H; TRIAZOLYLIDENE; IRIDIUM; 2,6-BIS(1,2,3-TRIAZOL-4-YL)PYRIDINE; 1,2,3-TRIAZOLYLIDENES;
D O I
10.1039/c9dt02614b
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Three Ru complexes containing carbohydrate/N-heterocyclic carbene hybrid ligands were synthesized that were comprised of a triazolylidene coordination site and a directly linked per-acetylated glucosyl (5Glc) or galactosyl unit (5Gal), or a glycosyl unit linked through an ethylene spacer (6). Electrochemical and UV-vis analysis indicate only minor perturbation of the electronic configuration of the metal center upon carbohydrate installation. Deprotection of the carbohydrate was accomplished under basic conditions to afford complexes that were stable in solution over several hours, but decomposed in the solid state. Complexes 5 and 6 were used as pre-catalysts for transfer hydrogenation of ketones under basic conditions, i.e. conditions that lead to in situ deprotection of the carbohydrate entity. The carbohydrate directly influences the catalytic activity of the metal center. Remotely linked carbohydrates (complex 6) induce significantly lower catalytic activity than directly linked carbohydrates (complexes 5Glc, 5Gal), while unfunctionalized triazolylidenes are an order of magnitude more active. These observations and substrate variations strongly suggest that substrate bonding is rate-limiting for transfer hydrogenation in these hybrid carbohydrate/triazolylidene systems.
引用
收藏
页码:11838 / 11847
页数:10
相关论文
共 79 条
  • [1] Grubbs' Ruthenium-Carbenes Beyond the Metathesis Reaction: Less Conventional Non-Metathetic Utility
    Alcaide, Benito
    Almendros, Pedro
    Luna, Amparo
    [J]. CHEMICAL REVIEWS, 2009, 109 (08) : 3817 - 3858
  • [2] 1,2,3-Triazolylidene ruthenium(II)(η6-arene) complexes: synthesis, metallation and reactivity
    Bagh, Bidraha
    McKinty, Adam M.
    Lough, Alan J.
    Stephan, Douglas W.
    [J]. DALTON TRANSACTIONS, 2014, 43 (34) : 12842 - 12850
  • [3] Fast transfer hydrogenation using a highly active orthometalated heterocyclic carbene ruthenium catalyst
    Baratta, W
    Schütz, J
    Herdtweck, E
    Herrmann, WA
    Rigo, P
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2005, 690 (24-25) : 5570 - 5575
  • [4] Mechanistic Studies on the Alkylation of Amines with Alcohols Catalyzed by a Bifunctional Iridium Complex
    Bartoszewicz, Agnieszka
    Miera, Greco Gonzalez
    Marcos, Rocio
    Norrby, Per-Ola
    Martin-Matute, Belen
    [J]. ACS CATALYSIS, 2015, 5 (06): : 3704 - 3716
  • [5] A Highly Active Bifunctional Iridium Complex with an Alcohol/Alkoxide-Tethered N-Heterocyclic Carbene for Alkylation of Amines with Alcohols
    Bartoszewicz, Agnieszka
    Marcos, Rocio
    Sahoo, Suman
    Inge, A. Ken
    Zou, Xiaodong
    Martin-Matute, Belen
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2012, 18 (45) : 14510 - 14519
  • [6] Tunable single-site ruthenium catalysts for efficient water oxidation
    Bernet, Lucile
    Lalrempuia, Ralte
    Ghattas, Wadih
    Mueller-Bunz, Helge
    Vigara, Laura
    Llobet, Antoni
    Albrecht, Martin
    [J]. CHEMICAL COMMUNICATIONS, 2011, 47 (28) : 8058 - 8060
  • [7] 'Click' chemistry in polymer and materials science
    Binder, Wolfgang H.
    Sachsenhofer, Robert
    [J]. MACROMOLECULAR RAPID COMMUNICATIONS, 2007, 28 (01) : 15 - 54
  • [8] Exploring the Scope of Pyridyl- and Picolyl-Functionalized 1,2,3-Triazol-5-ylidenes in Bidentate Coordination to Ruthenium(II) Cymene Chloride Complexes
    Bolje, Aljosa
    Hohloch, Stephan
    Urankar, Damijana
    Pevec, Andrej
    Gazvoda, Martin
    Sarkar, Biprajit
    Kosmrlj, Janez
    [J]. ORGANOMETALLICS, 2014, 33 (10) : 2588 - 2598
  • [9] Microwave assisted "click" chemistry for the synthesis of multiple labeled-carbohydrate oligonucleotides on solid support
    Bouillon, Camille
    Meyer, Albert
    Vidal, Sebastien
    Jochum, Anne
    Chevolot, Yann
    Cloarec, Jean-Pierre
    Praly, Jean-Pierre
    Vasseur, Jean-Jacques
    Morvan, Francois
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (12) : 4700 - 4702
  • [10] Formation of Self-Templated 2,6-Bis(1,2,3-triazol-4-yl)pyridine [2]Catenanes by Triazolyl Hydrogen Bonding: Selective Anion Hosts for Phosphate
    Byrne, Joseph P.
    Blasco, Salvador
    Aletti, Anna B.
    Hessman, Gary
    Gunnlaugsson, Thorfinnur
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (31) : 8938 - 8943