Reduction of Carbonyl Compounds by Hydrogen Transfer

Gladiali, Serafino; Taras, Rossana

doi:10.1002/9783527622115.ch6

Cited by 25 publications

(25 citation statements)

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“…In contrast, if a catalyst operates through a di-hydridic mechanism, the two hydrogen atoms coming from the donor scramble. Once the di-hydride complex is formed the two hydrogens are delivered from the active metal species to the carbonyl functionality indistinctly (Scheme 6) [8,35]. Scheme 5.…”

Section: Methodsmentioning

confidence: 99%

“…Additionally, formic acid can be activated with a weak base like triethylamine (formic acid:triethylamine mixtures are commercially available) and sometimes it can be used in aqueous solution or in biphasic systems. Unfortunately, the acidity of formic acid can, in several cases, inhibit or decompose the catalytic species, so its use is limited to these catalysts robust enough to survive in these conditions [8].…”

Section: Scheme 3 Transfer Hydrogenation From a Generic Donor Agent mentioning

confidence: 99%

“…This protocol is not the only synthetic route for obtaining carbinols from carbonyl compounds but its operational simplicity, the elimination of safety measures associated with the use of gaseous dihydrogen, the low cost of the reducing agents and the availability of a large number of catalysts of high activity and selectivity for the process, make this process of high interest [8].…”

Section: Introductionmentioning

confidence: 99%

“…The level of importance of such studies has been recognized in 2001 with the award of the Nobel prize in Chemistry [7].The catalyzed reduction of ketones in homogenous phase has increased in popularity during the last 50 years and the corresponding literature is very rich. The reaction involves a formal transfer of hydrogen from a donor (usually an alcohol) to an acceptor carbonyl compound (usually a ketone).This protocol is not the only synthetic route for obtaining carbinols from carbonyl compounds but its operational simplicity, the elimination of safety measures associated with the use of gaseous dihydrogen, the low cost of the reducing agents and the availability of a large number of catalysts of high activity and selectivity for the process, make this process of high interest [8].Many combinations of catalysts, hydrogen donors and acceptors have been developed during the last 25 years and most of them have been the objects of review articles [9].Nowadays, a large number of catalytic precursors for the reduction of ketones with elevated Turn Over Number (TON), Turn Over Frequency (TOF) and excellent enantiomeric excess (e.e.) are available and most of the chemistry of such catalysts has been studied in detail, including many mechanistic aspects.…”

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confidence: 99%

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Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

2020

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The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one of the most important routes for obtaining alcohols from carbonyl compounds. The interest of this method increases when opportune catalytic precursors are able to perform the transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied in terms of catalysts and variety of substrates. A large amount of information about the possible mechanisms is available nowadays, which has been of high importance for the development of systems with excellent outcomes in terms of conversion, enantioselectivity and Turn Over Frequency. On the other side, many mechanistic aspects are still unclear, especially for those catalytic precursors which have shown only moderate performances in transfer hydeogenation. This is the case of neutral [RuCl 2 (η 6 -arene)(P)] and cationic [Rh(PP) 2 ]X (X = anion; P and PP = monoand bidentate phosphine, respectively) complexes. Herein, a summary of the known information about the Transfer Hydrogenation catalyzed by these complexes is provided with a continuous focus on the more relevant mechanistic features. Abstract:The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one of the most important routes for obtaining alcohols from carbonyl compounds. The interest of this method increases when opportune catalytic precursors are able to perform the transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied in terms of catalysts and variety of substrates. A large amount of information about the possible mechanisms is available nowadays, which has been of high importance for the development of systems with excellent outcomes in terms of conversion, enantioselectivity and Turn Over Frequency. On the other side, many mechanistic aspects are still unclear, especially for those catalytic precursors which have shown only moderate performances in transfer hydeogenation. This is the case of neutral [RuCl2( 6 -arene)(P)] and cationic [Rh(PP)2]X (X = anion; P and PP = mono-and bidentate phosphine, respectively) complexes. Herein, a summary of the known information about the Transfer Hydrogenation catalyzed by these complexes is provided with a continuous focus on the more relevant mechanistic features.The possibility to reduce ketones to alcohols in an enantioselective way through ATH represents a milestone in the asymmetric catalysis, as chiral alcohols are employed as intermediates, as well as end-products in many industries, including fragrancies and pharmaceutics [2]. In addition, the protocol can be extended to a general C=X polar substrate (X = O, N), allowing the synthesis of chiral alcohols [2], amines, and many corresponding derivatives [3].Recent applications of such protocol have allowed the valorization of biomass by extracting lignin [4], or for the production of biofuels [5].Historically, a ...

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Section: Methodsmentioning

confidence: 99%

Section: Scheme 3 Transfer Hydrogenation From a Generic Donor Agent mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

2020

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“…TH is recognized as an efficient reduction method of unsaturated organic compounds (ketones, aldehydes, imines, olefins, etc.) and constitutes a safer alternative to the classical catalytic hydrogenations using highly flammable molecular hydrogen [38][39][40][41][42]. Replacing the most commonly employed hydrogen sources in TH reactions, i.e., 2-propanol or formic acid/triethylamine mixtures, by glycerol results not only economically appealing but also more environmentally friendly.…”

Section: Methodsmentioning

confidence: 99%

Glycerol: A promising Green Solvent and Reducing Agent for Metal-Catalyzed Transfer Hydrogenation Reactions and Nanoparticles Formation

2013

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Abstract:Glycerol is a non-toxic, non-hazardous, non-volatile, biodegradable, and recyclable liquid that is generated as a byproduct in the manufacture of biodiesel fuel from vegetable oils. Due to its easy availability, along with its unique combination of physical and chemical properties, glycerol has recently emerged as an economically appealing and safe solvent for organic synthesis. Recent works have also demonstrated that glycerol can be used as a hydrogen source in metal-catalyzed transfer hydrogenation of organic compounds, such as aldehydes, ketones, olefins and nitroarenes. Herein, the advances reached in this emerging field are reviewed. The utility of glycerol as solvent and reducing agent for the generation of metal nanoparticles is also briefly discussed.

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(R)- and (S)-2,2′-Bis(bis(3,5-dimethylphenyl)phosphanyl)-1,1′-binaphthalene

McWilliams

2015

Encyclopedia of Reagents for Organic Synthesis

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Reduction of Carbonyl Compounds by Hydrogen Transfer

Cited by 25 publications

References 85 publications

Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

Glycerol: A promising Green Solvent and Reducing Agent for Metal-Catalyzed Transfer Hydrogenation Reactions and Nanoparticles Formation

(R)- and (S)-2,2′-Bis(bis(3,5-dimethylphenyl)phosphanyl)-1,1′-binaphthalene

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