Rhodium(III) complexes containing the ligand 2,6-bis[4′-(S)-isopropyloxazolin-2′-yl]pyridine ((S,S)-iPr-pybox):: Efficient catalysts for asymmetric hydrosilylation of acetophenone

被引：13
|
作者：
Cuervo, D [1 ]
Gamasa, MP [1 ]
Gimeno, J [1 ]
机构：
[1] Univ Oviedo, Fac Quim, Unidad Asociada CSIC, Dept Quim Organ & Inorgan,Inst Univ Quim Organome, E-33071 Oviedo, Spain
来源：
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2006年 / 249卷 / 1-2期
关键词：
enantiopure pybox; hydrosilylation; rhodium; asymmetric catalysis;
D O I：
10.1016/j.molcata.2005.12.041
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The dinuclear complexes [Rh-2(mu-Cl)(2)(R)(2){(S,S)-Pr-i-pybox}(2)][BF4](2) (R=(E)-C(Me)=CH(Ph), C(Ph)=CH2) have been synthesized by the reaction of the complexes trans-[RhCl2(R){(S,S)-Pr-1-pybox}] (R=(E)-C(Me)=CH(Ph), C(Ph)=CH2) with AgBF4. The rhodium(III) complexes cis-[RhCl2(R){(S,S)-Pr-i-pybox}] (R=COPh, CH2C(Me)=CH2, CH2CH=CH2, CH2CH=CH(Ph), CH=C=CH2) and trans-[RhCl2{(E)C(Me)=CH(Ph)}{(S,S)-Pr-i-pybox}], recently reported, and the novel dinuclear complex [Rh-2(mu-Cl)(2){(E)-C(Me)=CH(Ph)}(2){(S,S)-Pr-i-pybox}21[BF4]2, exhibit high enantioselectivity in the hydrosilylation of acetophenone affording (S)-l-phenylethanol with high conversions and up to 89% ee. The species "RhCl{(S,S)-Pr-i-pybox}" is proposed as the real active rhodium catalyst and a pathway for its formation is also tentatively provided. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码：60 / 64
页数：5
相关论文
共 50 条
  • [1] One-pot stereoselective synthesis of organorhodium(III) complexes containing the chiral ligand 2,6-bis[4'-(S)-isopropyloxazolin-2'-yl]pyridine (iPr-pybox)
    Cuervo, D
    Díez, J
    Gamasa, MP
    Gimeno, J
    [J]. ORGANOMETALLICS, 2005, 24 (09) : 2224 - 2232
  • [2] Novel carbonyliridium and -rhodium complexes containing 2,6-bis[(4′S)-4′-isopropyloxazolin-2′-yl]pyridine (iPr-pybox) and 2,6-bis[(4′R)-4′-phenyloxazolin-2′-yl]pyridine (Ph-pybox) ligands
    Cuervo, D
    Díez, J
    Gamasa, MP
    Gimeno, J
    Paredes, P
    [J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2006, (03) : 599 - 608
  • [3] Rhodium(I) and rhodium(III) complexes containing the chiral ligand 2,6-bis[4′(S)-isopropyloxazolin-2′-yI]pyridine (pybox):: An unprecedented monohapto coordination of pybox
    Cuervo, D
    Díez, J
    Gamasa, MP
    García-Granda, S
    Gimeno, J
    [J]. INORGANIC CHEMISTRY, 2002, 41 (20) : 4999 - 5001
  • [4] Iridium(I) complexes bearing the (S,S)-iPr-pybox ligand in the asymmetric transfer hydrogenation of acetophenone
    de Julian, Eire
    Diez, Josefina
    Lastra, Elena
    Pilar Gamasa, M.
    [J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2014, 394 : 295 - 302
  • [5] Stereochemically controlled synthesis of Ruthenium(II) complexes containing bis(oxazolin-2′-yl)pyridine ligands.: X-ray crystal structures of trans-[RuCl2(PPh3){κ3-N,N,N-(S,S)-iPr-pybox}] and [RuCl(=C=C=CPh2)(PPh3){κ3-N,N,N-(S,S)-iPr-pybox}][PF6] ((S,S)-iPr-pybox=2,6-bis[4′-(S)-isopropyloxazolin-2′-yl]pyridine)
    Cadierno, V
    Gamasa, MP
    Gimeno, J
    Iglesias, L
    García-Granda, S
    [J]. INORGANIC CHEMISTRY, 1999, 38 (12) : 2874 - 2879
  • [6] Novel iridium complexes containing 2,6-bis(oxazoline)pyridine ligands:: Synthesis and reactivity of the diolefin iridium(I) complex [Ir(η2-C2H4)2{κ3N,N,N-(S,S)-i-Pr-pybox}][PF6] ((S,S)-i-Pr-pybox=2,6-Bis(4′-(S)-isopropyloxazolin-2′-yl)pyridine)
    Díez, J
    Gamasa, MP
    Gimeno, J
    Paredes, P
    [J]. ORGANOMETALLICS, 2005, 24 (08) : 1799 - 1802
  • [7] Copper(I) and silver(I) complexes containing the enantiopure N,N-bidentate 1,3-bis[4′-(S)-isopropyloxazolin-2′-yl]benzene ((S,S)-iPr-pheboxH) ligand
    Vega, Esmeralda
    de Julian, Eire
    Borrajo, Gustavo
    Diez, Josefina
    Lastra, Elena
    Pilar Gamasa, M.
    [J]. POLYHEDRON, 2015, 94 : 59 - 66
  • [8] Ethylene polymerization catalyzed by ruthenium and iron complexes containing 2,6-bis(2-oxazolin-2-yl)pyridine (pybox) ligand-cocatalyst system
    [J]. 1600, Chemical Soc of Japan, Tokyo, Japan (73):
  • [9] Ethylene polymerization catalyzed by ruthenium and iron complexes containing 2,6-bis(2-oxazolin-2-yl)pyridine (Pybox) ligand-cocatalyst system
    Nomura, K
    Sidokmai, W
    Imanishi, Y
    [J]. BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2000, 73 (03) : 599 - 605
  • [10] Preparation, structures, and properties of nickel complexes containing 2,6-bis[4', 4'-dimethyloxazolin-2'-yl] pyridine, a pincer ligand
    Jia, Wei-Guo
    Li, Dan-Dan
    Yan, Li-Qin
    Sheng, En-Hong
    Dai, Yuan-Chen
    [J]. JOURNAL OF COORDINATION CHEMISTRY, 2014, 67 (02) : 363 - 371
12345