Novel P-stereogenic PCP pincer-aryl ruthenium(II) complexes and their use in the asymmetric hydrogen transfer reaction of acetophenone

被引:63
|
作者
Medici, S
Gagliardo, M
Williams, SB
Chase, PA
Gladiali, S
Lutz, M
Spek, AL
van Klink, GPM
van Koten, G
机构
[1] Univ Utrecht, Bijvoet Ctr Biomol Res, Dept Crystal & Struct Chem, NL-3584 CH Utrecht, Netherlands
[2] Univ Utrecht, Debye Inst, Dept Met Mediated Synth, NL-3584 CH Utrecht, Netherlands
[3] Univ Sassari, Dipartimento Chim, I-07100 Sassari, Italy
关键词
D O I
10.1002/hlca.200590048
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Achiral P-donor pincer-aryl ruthenium complexes ([RuCl(PCP)(PPh3)]) 4c,d were synthesized via transcyclometalation reactions by mixing equivalent amounts of [1,3-phenylenebis(methylene)]bis[diisopropylphosphine] (2c) or [1,3-phenylenebis(methylene)]bis[diphenylphosphine] (2d) and the N-donor pincer-aryl complex [RuCl{2,6-(Me2NCH2)(2)C6H3}(PPh3)], (3; Scheme 2). The same synthetic procedure was successfully applied for the preparation of novel chiral P-donor pincer-aryl ruthenium complexes [RuCl(P*CP*)(PPh3)] 4a,b by reacting P-stereogenic pincer-arenes (S, S)-[1,3-phenylenebis(methylene)]bis[ (alkyl)(phenyl)phosphines] 2a,b (alkyl = Pr-i or Bu-t, P*CHP*) and the complex [RuCl{2,6-(Me2NCH2)(2)C6H3}(PPh3)], (3; Scheme 3). The crystal structures of achiral [RuCl((PCP)-P-iPr,iPr)(PPh3)] 4c and of chiral (S,S)-[RuCl-((PCP)-P-tBu,Ph)(PPh3)] 4a were determined by X-ray diffraction (Fig. 3). Achiral [RuCl(P*CP*)(PPh3)] complexes and chiral [RuCl(P*CP*)(PPh3)] complexes were tested as catalyst in the H-transfer reduction of acetophenone with propan-2-ol. With the chiral complexes, a modest enantioselectivity was obtained.
引用
收藏
页码:694 / 705
页数:12
相关论文
共 48 条
  • [21] Hydrogenation of imines catalyzed by ruthenium(II) complexes containing phosphorus-nitrogen ligands via hydrogen transfer reaction
    Aranda, Braulio
    Valdebenito, Gonzalo
    Parra-Melip, Sebastian
    Lopez, Vicente
    Moya, Sergio
    Vega, Andres
    Aguirre, Pedro
    MOLECULAR CATALYSIS, 2022, 526
  • [22] Asymmetric transfer hydrogenation of acetophenone derivatives using 2-benzyl-tethered ruthenium (II)/TsDPEN complexes bearing η6-(p-OR) (R = H, iPr, Bn, Ph) ligands
    Knighton, Richard C.
    Vyas, Vijyesh K.
    Mailey, Luke H.
    Bhanage, Bhalchandra M.
    Wills, Martin
    JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2018, 875 : 72 - 79
  • [23] Ruthenium(II) complexes containing optically active hemilabile P,N,O-tridentate ligands. Synthesis and evaluation in catalytic asymmetric transfer hydrogenation of acetophenone by propan-2-ol
    Yang, H
    AlvarezGressier, M
    Lugan, N
    Mathieu, R
    ORGANOMETALLICS, 1997, 16 (07) : 1401 - 1409
  • [24] Half-sandwich ruthenium(II) and rhodium(III) complexes bearing chiral amino-phosphoramidite ligands: Synthesis, characterization and application in asymmetric transfer hydrogenation of acetophenone
    Arena, Carmela Grazia
    Cuzzola, Angela
    Drommi, Dario
    POLYHEDRON, 2012, 48 (01) : 221 - 226
  • [25] Synthesis and Structures of Arene Ruthenium (II)-NHC Complexes: Efficient Catalytic α-alkylation of ketones via Hydrogen Auto Transfer Reaction
    Balamurugan, Gunasekaran
    Balaji, Sundarraman
    Ramesh, Rengan
    Bhuvanesh, Nattamai S. P.
    APPLIED ORGANOMETALLIC CHEMISTRY, 2019, 33 (01)
  • [26] Stereoelectronic Factors in Iron Catalysis: Synthesis and Characterization of Aryl-Substituted Iron(II) Carbonyl P-N-N-P Complexes and Their Use in the Asymmetric Transfer Hydrogenation of Ketones
    Sues, Peter E.
    Lough, Alan J.
    Morris, Robert H.
    ORGANOMETALLICS, 2011, 30 (16) : 4418 - 4431
  • [27] Chiral (η6-p-Cymene)ruthenium(II) Complexes Containing Monodentate Acylthiourea Ligands for Efficient Asymmetric Transfer Hydrogenation of Ketones
    Sheeba, Mani Mary
    Tamizh, Manoharan Muthu
    Farrugia, Louis J.
    Endo, Akira
    Karvembu, Ramasamy
    ORGANOMETALLICS, 2014, 33 (02) : 540 - 550
  • [28] Use of surfactants in water-soluble ruthenium(II) complex-catalyzed asymmetric hydrogen-transfer reduction of aromatic ketones
    Rhyoo, HY
    Park, HJ
    Suh, WH
    Chung, YK
    TETRAHEDRON LETTERS, 2002, 43 (02) : 269 - 272
  • [29] SYNTHESES OF SOME TRIPLE CHLORO-BRIDGED COMPLEXES OF RUTHENIUM(II) INCLUDING A NOVEL PHOSPHINE LIGAND TRANSFER-REACTION
    HEAD, RA
    NIXON, JF
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1975, (04) : 135 - 136
  • [30] Synthesis of half-sandwich ruthenium(II) and iridium(III) complexes containing imidazole-based phosphinite ligands and their use in catalytic transfer hydrogenation of acetophenone with isopropanol
    Isik, Ugur
    Meric, Nermin
    Kayan, Cezmi
    Kilic, Ahmet
    Belyankova, Yelizaveta
    Zazybin, Alexey
    Aydemir, Murat
    JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2023, 998