Hydrogenolyse von Trimethylsilylenolethern unter Verwendung eines sauren Rutheniumdiwasserstoff‐Komplexes als Katalysator

Die heterolytische Spaltung von H2ist der Schlusselschritt in der durch [RuCl(η2-H2)(dppe)2]OTf (dppe=1,2-Bis(diphenylphosphanyl)ethan, OTf=Trifluormethansulfonat) katalysierten Hydrogenolyse von Trimethylsilylenolethern, bei der ein Keton und Me3SiH die Produkte sind (siehe Schema). Die ebenfalls beschriebene stochiometrische, Ruthenium-unterstutzte Protonierung eines prochiralen Lithiumenolats mit H2 liefert hochenantioselektiv das chirale Keton (bis 75% ee).

[1]  Zhenyang Lin,et al.  Theoretical studies of the acidity of the dihydrogen complexes trans-[LM(H2PCH2CH2PH2)(2)(eta(2)-H-2)](n+) , 1999 .

[2]  D. Roddick,et al.  Protonation and H2 Heterolysis Reactions of Electrophilic (η5-C5R5)Ru(dfepe)(X) (R = H, Me; X = H, OTf) Complexes , 1998 .

[3]  V. Bakhmutov,et al.  NMR evidence for formation of new alcohol rhenium complexes as intermediates in ionic hydrogenations of carbonyl groups with systems composed of ReH2(NO)(CO)(PR3)2 (R = Pri, CH3, OPri) and CF3COOH , 1998 .

[4]  B. Chaudret,et al.  Quantum Mechanical Exchange Coupling in Polyhydride and Dihydrogen Complexes. , 1998, Chemical reviews.

[5]  Kwok‐yin Wong,et al.  Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO2 to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes , 1998 .

[6]  R. Kuwano,et al.  Catalytic Asymmetric Synthesis of β-Hydroxy-α-amino Acids: Highly Enantioselective Hydrogenation of β-Oxy-α-acetamidoacrylates , 1998 .

[7]  R. Crabtree Recent advances in hydrogen bonding studies involving metal hydrides , 1998 .

[8]  Miguel A. Esteruelas,et al.  Dihydrogen Complexes as Homogeneous Reduction Catalysts. , 1998, Chemical reviews.

[9]  Iwai,et al.  Bimetallic system for nitrogen fixation: ruthenium-assisted protonation of coordinated N2 on tungsten with H2 , 1998, Science.

[10]  K. Ishihara,et al.  Asymmetric Protonations of Enol Derivatives , 1997 .

[11]  C. Lau,et al.  Syntheses and Characterization of Hydrotris(1-pyrazolyl)borate Dihydrogen Complexes of Ruthenium and Their Roles in Catalytic Hydrogenation Reactions , 1997 .

[12]  C. Fehr Enantioselective Protonation of Enolates and Enols , 1996 .

[13]  Ch. Fehr Enantioselektive Protonierung von Enolaten und Enolen , 1996 .

[14]  R. Morris 1995 Alcan Award Lecture New intermediates in the homolytic and heterolytic splitting of dihydrogen , 1996 .

[15]  V. Day,et al.  Coupling H2 to Electron Transfer with a 17-Electron Heterobimetallic Hydride: A “Redox Switch” Model for the H2-Activating Center of Hydrogenase , 1996 .

[16]  R. Morris,et al.  Influence of Chloride versus Hydride on H-H Bonding and Acidity of the Trans Dihydrogen Ligand in the Complexes trans-[Ru(H2)X(PR2CH2CH2PR2)2]+, X = Cl, H, R = Ph, Et. Crystal Structure Determinations of [RuCl(dppe)2]PF6 and trans-[Ru(H2)Cl(dppe)2]PF6 , 1994 .

[17]  R. Morris,et al.  Effect of the Ligand and Metal on the pKa Values of the Dihydrogen Ligand in the Series of Complexes [M(H2)H(L)2]+, M = Fe, Ru, Os, Containing Isosteric Ditertiaryphosphine Ligands, L , 1994 .

[18]  R. Hembre,et al.  Hydrogenase Enzyme Reactivity Modeling with a Transition-Metal Dihydrogen Complex , 1994 .

[19]  D. Heinekey,et al.  Coordination chemistry of dihydrogen , 1993 .

[20]  P. Jessop,et al.  Reactions of transition metal dihydrogen complexes , 1992 .

[21]  M. Peruzzini,et al.  A deceptively simple case of selective hydrogenation of phenylacetylene to styrene catalyzed by a cis-hydrido(.eta.2-dihydrogen)ruthenium(II) complex , 1992 .

[22]  M. Schulz,et al.  Hydrogenation of benzylideneacetone catalyzed by chlorodihydridobis(diisopropylphosphine)iridium: kinetic evidence for the participation of an iridium-.eta.2-dihydrogen complex in the activation of molecular hydrogen , 1992 .

[23]  M. Peruzzini,et al.  Selective hydrogenation of 1-alkynes to alkenes catalyzed by an iron(II) cis-hydride .eta.2-dihydrogen complex. A case of intramolecular reaction between .eta.2-H2 and .sigma.-vinyl ligands , 1992 .

[24]  Harvey J. Wasserman,et al.  Characterization of the first examples of isolable molecular hydrogen complexes, M(CO)3(PR3)2(H2) (M = molybdenum or tungsten; R = Cy or isopropyl). Evidence for a side-on bonded dihydrogen ligand , 1984 .

[25]  T. Tidwell,et al.  Mechanistic change in acid-catalyzed hydrolysis of silyl vinyl ethers , 1980 .

[26]  T. Saegusa,et al.  Synthesis of .alpha.,.beta.-unsaturated carbonyl compounds by palladium(II)-catalyzed dehydrosilylation of silyl enol ethers , 1978 .