Catalytic isomerization of allylic alcohols by (η6-p-cymene)-ruthenium(II) complexes in organic and aqueous media:: New recyclable and highly efficient catalysts in water containing ammonium-functionalized ligands

被引:59
作者
Crochet, P [1 ]
Díez, J [1 ]
Fernández-Zúmel, MA [1 ]
Gimeno, J [1 ]
机构
[1] Univ Oviedo, Dept Quim Organ & Inorgan, Inst Univ Quim Organomet Enrique Moles, Unidad Asociada,CSIC,Fac Quim, E-33071 Oviedo, Spain
关键词
allylic alcohol; ammonium ligands; isomerization; recycling; ruthenium; water-soluble;
D O I
10.1002/adsc.200505279
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
The water-soluble complexes [RuCl2(eta(6)-p-cymene){kappa-(P)-PPh3-n(OCH2CH2NMe3)(n)}][SbF6](n) [n = 1 (4a), 2 (4b) or 3 (4c)] have been prepared from the neutral precursors [RuCl2(eta(6)-p-cymene){kappa-(P)-PPh3-n(OCH2CH2NMe2)(n)}] [n = 1 (2a), 2 (2b) or 3 (2c)] and MeI via quaternization of the nitrogen atom of the terminal aminoalkyl groups, and subsequent counteranion exchange by the treatment with AgSbF6. Complexes 2a-c and 4a-c have proven to be highly active catalysts for isomerization of allylic alcohols in THF and aqueous media, respectively. Moreover, the water-soluble catalysts 4a-c can be reused after a simple extraction process at the end of the reaction. In particular, 4c presents a remarkable capability to be recycled, being active during 10 successive runs.
引用
收藏
页码:93 / 100
页数:8
相关论文
共 62 条
[31]   Stereoselective organic reactions in water [J].
Lindström, UM .
CHEMICAL REVIEWS, 2002, 102 (08) :2751-2771
[32]  
LUBINEAU A, 1994, SYNTHESIS-STUTTGART, P741
[33]   Water-soluble ruthenium alkylidenes: Synthesis, characterization, and application to olefin metathesis in protic solvents [J].
Lynn, DM ;
Mohr, B ;
Grubbs, RH ;
Henling, LM ;
Day, MW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (28) :6601-6609
[34]   Living ring-opening metathesis polymerization in water [J].
Lynn, DM ;
Mohr, B ;
Grubbs, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (07) :1627-1628
[35]   Highly efficient redox isomerization of allylic alcohols at ambient temperature catalyzed by novel ruthenium-cyclopentadienyl complexes-new insight into the mechanism [J].
Martín-Matute, B ;
Bogár, K ;
Edin, M ;
Kaynak, FB ;
Bäckvall, JE .
CHEMISTRY-A EUROPEAN JOURNAL, 2005, 11 (20) :5832-5842
[36]   THE MECHANISM OF AQUEOUS RUTHENIUM(II)-CATALYZED OLEFIN ISOMERIZATION [J].
MCGRATH, DV ;
GRUBBS, RH .
ORGANOMETALLICS, 1994, 13 (01) :224-235
[37]   AQUEOUS RUTHENIUM(II) COMPLEXES OF FUNCTIONALIZED OLEFINS - THE X-RAY STRUCTURE OF RU(H2O)2(ETA-1(O) - ETA-2(C,C')-OCOCH2CH=CHCH3)2 [J].
MCGRATH, DV ;
GRUBBS, RH ;
ZILLER, JW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (09) :3611-3613
[38]   Synthesis of water-soluble, aliphatic phosphines and their application to well-defined ruthenium olefin metathesis catalysts [J].
Mohr, B ;
Lynn, DM ;
Grubbs, RH .
ORGANOMETALLICS, 1996, 15 (20) :4317-4325
[39]   ENANTIOSELECTIVE CATALYTIC-HYDROGENATION OF ALPHA-(ACETYLAMINO)CINNAMIC ACID WITH A RHODIUM PHOSPHANE COMPLEX IN AQUEOUS-SOLUTION [J].
NAGEL, U ;
KINZEL, E .
CHEMISCHE BERICHTE-RECUEIL, 1986, 119 (05) :1731-1733
[40]   Homogeneous catalysts based on water-soluble phosphines [J].
Pinault, N ;
Bruce, DW .
COORDINATION CHEMISTRY REVIEWS, 2003, 241 (1-2) :1-25