Catalytic Hydrogenation of Esters. Development of an Efficient Catalyst and Processes for Synthesising (<i>R</i>)-1,2-Propanediol and 2-(<i>l</i>-Menthoxy)ethanol

Kuriyama, Wataru; Matsumoto, T.; Ogata, Osamu; Ino, Yasunori; Aoki, Kuriko; Tanaka, Shigeru; Ishida, Kenya; Kobayashi, Tohru; Sayo, Noboru; Saito, Takao

doi:10.1021/op200234j

Cited by 276 publications

(251 citation statements)

References 31 publications

(14 reference statements)

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“…As proposed by Kuriyama et al, we also surmise that in the presence of CO, an equilibrium between the monocarbonyl RuH(CO)(HN(CH 2 CH 2 PPh 2 ) 2 ) + and dicarbonyl complex, RuH(CO) 2 (HN(CH 2 CH 2 PPh 2 ) 2 ) + is possible . 22 Therefore, RuH(CO) 2 (HN(CH 2 CH 2 PPh 2 ) 2 ) + is probably the resting state of the catalytic cycle. Interestingly, although PEHA can act as potential multidentate nitrogen donor ligand to the Ru center, no ligand exchange occurred under the reaction conditions, as evidenced by the absence of free PNP ligand signal in 31 P NMR.…”

Section: Table 2 Extended-time Study At 145 and 125 °Cmentioning

confidence: 99%

Conversion of CO₂ from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

et al. 2016

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A highly efficient homogeneous catalyst system for the production of CH3OH from CO2 using pentaethylenehexamine and Ru-Macho-BH (1) at 125-165 °C in an ethereal solvent has been developed (initial turnover frequency = 70 h(-1) at 145 °C). Ease of separation of CH3OH is demonstrated by simple distillation from the reaction mixture. The robustness of the catalytic system was shown by recycling the catalyst over five runs without significant loss of activity (turnover number > 2000). Various sources of CO2 can be used for this reaction including air, despite its low CO2 concentration (400 ppm). For the first time, we have demonstrated that CO2 captured from air can be directly converted to CH3OH in 79% yield using a homogeneous catalytic system.

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Section: Table 2 Extended-time Study At 145 and 125 °Cmentioning

confidence: 99%

Conversion of CO₂ from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

et al. 2016

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“…Note that the welld escribed Ru-MACHO-BH catalyst does not facilitate the homogeneous hydrogenation of substrate 4n to 5n. [10] Thev ersatility of complex 3 as efficienta nd selective homogeneoush ydrogenation catalyst was further demonstrated in the preparation of diols from diesters and lactones, respectively.A romatic diesters such as dimethylt erephthalate (4o)a nd naphthalene 2,6-dimethylc arboxylate (4p)w ere cleanly reduced to form the diols in good yields.I nterestingly,t he catalytic systemi st olerant towards the pyridine ring in compound 4q and almost quantitative product formation was observedu ponr eactionw ith H 2 gas (Table 3, entry 3). Comparable results were found with the aliphatic dimethyls uccinate (Table 3, entry 4).…”

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confidence: 99%

“…[4] In the early 2000s av ariety of seminal reportso n homogeneous catalysts for the hydrogenation of estersa ppeared in the literature. [5][6][7] Major developments in this field were madeb yt he groups of Milstein, [8] Saudan, [9] Kuriyama, [10] andG usev. [11] In addition, very recently ah ighly active bis-NHC amino pincerR uc omplexh as been developed for ester hydrogenation.…”

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confidence: 99%

Improved Second Generation Iron Pincer Complexes for Effective Ester Hydrogenation

et al. 2016

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Hydrogenation of esterst oa lcoholsw ith aw ell-definedi ron iPr2 PNP pincerc omplexh as been recently reported by us and other groups.W en ow introduce an ovel and sterically less hindered Et2 PNP congener that provides superior catalytic activity in the hydrogenation of various carboxylic acid esters and lactones comparedt ot he known complex. Successful hydrogenation proceeds under relatively mild conditions (60 8 8C) with lower catalyst loadings.Keywords: alcohols;c atalytic hydrogenation;esters; iron;p incer complexes Thec atalytic hydrogenation of esterst ot he corresponding alcohols represents an interesting methodology of paramount importance for organic synthesis and fine chemical processes.[1] In the past, this transformation relied on the use of stoichiometrica mounts of inorganic metal hydridess uch as LiAlH 4 ,N aBH 4 and related compounds resulting in the formation of stoichiometrica mounts of waste products followed by complexw ork-upp rocedures .[2] In contrast, catalytic hydrogenation of esters and lactonese mploying H 2 constitutes ac ompletely atom economic, waste-free and environmentally benign transformation. Heterogeneousc atalysts are applied in the hydrogenation of fatty estersb ut these catalysts require high temperature andp ressure.[3] Hence,t he development of milder and more selective catalytic protocols for ester hydrogenation facilitated by well-defined homogeneous complexes constitutes an actual and highly desired research goal. [4] In the early 2000s av ariety of seminal reportso n homogeneous catalysts for the hydrogenation of estersa ppeared in the literature. [5][6][7] Major developments in this field were madeb yt he groups of Milstein, [8] Saudan, [9] Kuriyama, [10] andG usev. [11] In addition, very recently ah ighly active bis-NHC amino pincerR uc omplexh as been developed for ester hydrogenation. [12] Despite the recent progress with these Ru-based materials,t he development of inexpensive,e arthabundant metal catalysts is desirable.I nt his context, iron-based catalysts are of special interest due to their low cost, low toxicity and high abundance. [13] In the past year, significant advancesh ave been achieved in our group [14] ando thers [15] using well-defined ironbased pincerc omplexes (Figure 1), which were successfullya pplied in selective hydrogenation and dehydrogenation reactions.[16] Based on our experience in this redox catalysis, [17] we became interested in the development of similar applications using an iron-based catalyst.Inspired by our recent worko nt he hydrogenation of esters to alcohols [14b] conducted with the isopropyltaggedi ron-PNP pincerc omplex 1,w ef ocused on the preparation of two novelc ongeners 2 and 3 bearing phosphinem otifsw ith different stericd emands (Figure 2). Herein, we address the influence of the alkyl substituents at the phosphorus binding site on

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“…I should note that by the time we had got round to publish these improved protocols, a number of interesting ester hydrogenation catalysts had appeared, many of which use (different) tridentate ligands including an amine function. 22,39,40 Takasago International Corporation have recently reported a ton-scale ester hydrogenation using a new ruthenium-PNP catalyst. 40 We will soon report several related catalysts that work pretty well, but we also believe the scope and application of ester hydrogenation needs to be fully studied, so that the synthetic community adopt this greener reaction protocol in target synthesis.…”

Section: Figurementioning

confidence: 99%

Catalytic Hydrogenation of Low-Reactivity Carbonyl Groups Using Bifunctional Chiral Tridentate Ligands

Clarke

2014

Synlett

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This account describes studies on the catalytic hydrogenation of carbonyl groups that are not readily reduced. The development of well-defined chiral phosphine-diamine ruthenium catalysts for hydrogenation of ketones and esters is described. These chiral catalysts promote the hydrogenation of ketones functionalised with tertiary alkyl and gem-dimethyl groups with enantioselectivities of up to 98% ee. They also reduce a range of heterocyclic and nitrilefunctionalised ketones that react slowly with or inhibit other catalysts. Changing from ruthenium to iridium complexes gives highly selective catalysts that also hydrogenate (the more reactive) secondary alkyl functionalised ketones, including those with unprotected amines. These catalysts operate rapidly at room temperature, require low catalysts loadings, and deliver up to 98% ee. Achiral variants of these catalysts also promote the hydrogenation of esters under mild conditions. This account also describes our studies that shed light on the mechanism of action of these catalysts, and a stereochemical model is proposed.

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Catalytic Hydrogenation of Esters. Development of an Efficient Catalyst and Processes for Synthesising (R)-1,2-Propanediol and 2-(l-Menthoxy)ethanol

Cited by 276 publications

References 31 publications

Conversion of CO₂ from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

Conversion of CO₂ from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

Improved Second Generation Iron Pincer Complexes for Effective Ester Hydrogenation

Catalytic Hydrogenation of Low-Reactivity Carbonyl Groups Using Bifunctional Chiral Tridentate Ligands

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Catalytic Hydrogenation of Esters. Development of an Efficient Catalyst and Processes for Synthesising (R)-1,2-Propanediol and 2-(l-Menthoxy)ethanol

Cited by 276 publications

References 31 publications

Conversion of CO2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

Conversion of CO2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

Improved Second Generation Iron Pincer Complexes for Effective Ester Hydrogenation

Catalytic Hydrogenation of Low-Reactivity Carbonyl Groups Using Bifunc­tional Chiral Tridentate Ligands

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Conversion of CO₂ from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

Conversion of CO₂ from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst

Catalytic Hydrogenation of Low-Reactivity Carbonyl Groups Using Bifunctional Chiral Tridentate Ligands