Transfer Hydrogenation of Carbonyl Compounds Catalyzed by a Ruthenium−Acetamido Complex:  Evidence for a Stepwise Hydrogen Transfer Mechanism

2001 ◽  
Vol 20 (17) ◽  
pp. 3641-3643 ◽  
Author(s):  
Chae S. Yi ◽  
Zhengjie He ◽  
Ilia A. Guzei
Keyword(s):  
Carbonyl Compounds ◽  
Hydrogen Transfer ◽  
Transfer Mechanism ◽  
Transfer Hydrogenation

Transfer Hydrogenation of Carbonyl Compounds and Alkenes Catalyzed by Ruthenium(II)-N-Heterocycle Carbene Complexes

2007 ◽  
Vol 72 (8) ◽  
pp. 1037-1045 ◽  
Author(s):  
Marianna Fekete ◽  
Ferenc Joó
Keyword(s):  
Carbonyl Compounds ◽  
Hydrogen Transfer ◽  
Transfer Hydrogenation ◽  
Unsaturated Alcohol ◽  
Two Phase ◽  
Carbene Complexes ◽  
Saturated Alcohol ◽  
Catalytic Activities ◽  
Saturated Aldehyde ◽  
Phase Mixture

The Ru(II)-N-heterocycle carbene complexes [RuCl2(η6-p-cymene)L] (L = 1-butyl-3-methylimid- azol-2-ylidene) and [RuCl(η6-p-cymene)L(pta)]Cl (pta = 1,3,5-triaza-7-phosphaadamantane) showed excellent catalytic activities (with turnover frequencies up to 1116 h-1) in the hydrogen transfer reduction of cinnamaldehyde and several ketones using propan-2-ol/KOH as a H-donor. Similar hydrogenations of trans-stilbene and cyclohexene were characterized by low conversions. The hydrogenation of 4-phenylbut-3-en-2-one and cinnamaldehyde proceeded with moderate selectivities of the formation of the saturated alcohol or of the of C=C hydrogenation (giving saturated ketone or saturated aldehyde). In the case of cinnamaldehyde, the unsaturated alcohol is initially formed; however, subsequent redox isomerization to the saturated aldehyde with the same catalyst diminishes its yield. The hydrogen transfer from formate to 4-phenylbut-3-en-2-one in an aqueous-organic two-phase mixture was also demonstrated.

scholarly journals New Bifunctional Bis(azairidacycle) with Axial Chirality via Double Cyclometalation of 2,2′-Bis(aminomethyl)-1,1′-binaphthyl

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1165
Author(s):  
Yasuhiro Sato ◽  
Yuichi Kawata ◽  
Shungo Yasui ◽  
Yoshihito Kayaki ◽  
Takao Ikariya
Keyword(s):  
Hydrogen Transfer ◽  
Bond Cleavage ◽  
Enantiomeric Excess ◽  
Transfer Hydrogenation ◽  
Catalyst Precursor ◽  
Asymmetric Catalysts ◽  
Axially Chiral ◽  
Diastereomeric Mixture ◽  
Raney Ni ◽  
Half Sandwich

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2′-bis(aminomethyl)-1,1′-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = η5–C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium complexes (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to a catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to an enantiomeric excess (ee) of 67%.

A CONVENIENT “HYDROGEN TRANSFER” HYDROGENATION OF TESTOSTERONE

1989 ◽  
Vol 21 (4) ◽  
pp. 515-517 ◽  
Author(s):  
Dimitris M. Spyriounis ◽  
George Ikonomidis ◽  
Vassilis J. Demopoulos
Keyword(s):  
Hydrogen Transfer ◽  
Transfer Hydrogenation

Recyclable Covalent Triazine Framework-based Ru Catalyst for Transfer Hydrogenation of Carbonyl Compounds in Water

2019 ◽  
Vol 7 (9) ◽  
pp. 8893-8899 ◽  
Author(s):  
Sudakar Padmanaban ◽  
Gunniya Hariyanandam Gunasekar ◽  
Mearae Lee ◽  
Sungho Yoon
Keyword(s):  
Carbonyl Compounds ◽  
Transfer Hydrogenation ◽  
Ru Catalyst ◽  
Covalent Triazine Framework

scholarly journals Catalytic Activity of High-Surface-Area Amorphous MgO Obtained from Upsalite

Catalysts ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 1338
Author(s):  
Marek Gliński ◽  
Ewa M. Iwanek (nee Wilczkowska) ◽  
Urszula Ulkowska ◽  
Agnieszka Czajka ◽  
Zbigniew Kaszkur
Keyword(s):  
Surface Area ◽  
Carbonyl Compounds ◽  
Main Product ◽  
High Surface ◽  
High Surface Area ◽  
Hydrogenation Reaction ◽  
Transfer Hydrogenation ◽  
Reaction Conditions ◽  
Synthesis Conditions ◽  
Transfer Hydrogenation Reaction

The first aim of the research was to synthesize a pure Upsalite, which is an amorphous form of MgCO3, by modifying a procedure described in the literature, so that it would be the precursor of a high-surface, amorphous magnesium oxide. The results indicate that within the studied reaction conditions, the type of alcohol used as the reactant has the most pronounced effect on the yield of reaction. From the two alcohols that led to the highest yield of Upsalite, methanol gave a substantially larger surface area (794 vs. 191 m2 g−1). The optimized synthesis conditions of Upsalite were used to obtain MgO via thermolysis, whose activity in the transfer hydrogenation reaction (THR) from ethanol, 2-propanol and 2-pentanol to various carbonyl compounds was determined. The optimal conditions for the thermolysis were as follows: vacuum, T = 673 K as the final temperature, and a heating rate of 2 deg min−1. The high-surface, amorphous magnesia (SBET = 488 m2 g−1) was found to be a very selective catalyst to 4-t-butylcyclohexanone in THR, which led to a diastereoselectivity of over 94% to the E-isomer of 4-t-butylcyclohexanol for more than 3 h, with conversions of up to 97% with either 2-propanol or 2-pentanol as the hydrogen donor. In the case of acrolein and 2-n-propylacrolein being used as the hydrogen acceptors, the unsaturated alcohol (UOL) was the main product of the reaction, with higher UOL yields noted for ethanol than 2-propanol.

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