Chemoselective Transfer Hydrogenation of α,β-Unsaturated Aldehydes to Allylic Alcohols Using Formic Acid Catalyzed by Polymer-Bound Rh Carbonyl Clusters

Mizugaki, Tomoo; Kanayama, Y; Ebitani, Kohki; Kaneda, Kiyotomi

doi:10.1021/jo9719362

Cited by 46 publications

(22 citation statements)

References 8 publications

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“…These catalysts may be superior to the traditional heterogeneous catalysts in terms of reactivity and selectivity, but benefit over homogeneous catalysts in their ease of removal and re-use. Similar immobilizations have involved the binding of rhodium carbonyl clusters to polymers [15,16]. Generally high selectivity was observed in the hydrogenation of a series of unsaturated aldehydes either under hydrogen and carbon monoxide or formic acid transfer hydrogenations.…”

Section: Cationic Rhodium Phosphine Catalystsmentioning

confidence: 97%

“…The rhodium carbonyl cluster [Rh 6 (CO) 16 ], in combination with the diamine N,N,N',N'-tetramethyl-1,3-propanediamine is an effective catalytic system for the 15 hydrogenation of saturated and unsaturated aldehydes in water under a pressure of carbon monoxide and hydrogen [11]. In reactions lasting only a few hours, and using a substrate catalyst ratio of 300, simple aldehydes are converted in quantitative yields.…”

Section: Rh-amine Catalystsmentioning

confidence: 99%

“…Three catalysts were investigated, namely [Co 2 (CO) 8 ], [Co(CO) 8 /PBu n 3 ], and [Rh 6 (CO) 16 ]. The [Co(CO) 8 /PBu n 3 ] catalyst showed activity for reductive amination using ammonia and aromatic amines.…”

Section: Reductive Amination Of Ketones and Aldehydesmentioning

confidence: 99%

“…The [Co(CO) 8 /PBu n 3 ] catalyst showed activity for reductive amination using ammonia and aromatic amines. The [Rh 6 (CO) 16 ] catalyst could be used for reductive amination using the more basic aliphatic amines that were found to poison the cobalt catalyst. This early report pointed out that the successful reductive amination of iso-butanal (Me 2 CCHO) with piperidine involves selective enamine hydrogenation, that reductive amination of cyclohexanone with isopropylamine probably involves imine hydrogenation, and that reductive amination of benzaldehyde with piperidine would presumably involve the reduction of a carbinolamine.…”

Section: Reductive Amination Of Ketones and Aldehydesmentioning

confidence: 99%

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Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Clarke¹,

Roff²

2006

The Handbook of Homogeneous Hydrogenation

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414Scheme 15.1 Hydrogenation of n-butyraldehyde. Table 15.1 Hydrogenation of aldehydes with [IrH 3 (PPh 3 ) 3 ] in acetic acid. Substrate Catalyst [mol.%] Temperature [8C] Yield [%] TON TOF [h -1 ] 0.022 80 73 3280 492 0.023 110 82 3540 177 0.032 90 64 2000 89 0.039 110 80 2030 81 0.013 110 98 7780 259 examined for a,b-unsaturated aldehydes (Scheme 15.2). Using the [IrH 3 (PPh 3 ) 3 ] complex in acetic acid for the hydrogenation of crotonaldehyde resulted in the formation of the saturated alcohol (Scheme 15.3). It was also noted that this catalyst did not allow for ketone hydrogenation at 10 bar. Other attempts to use iridium PPh 3 complexes such as [IrCl(PPh 3 ) 3 ], [IrCl(CO)(PPh 3 ) 2 ], [Ir(ClO 4 )(CO)(PPh 3 ) 2 ] and [Ir(CO)(PPh 3 ) 3 ]ClO 4 to hydrogenate unsaturated aldehydes did not yield great results [3], mainly because these catalysts suffered from low activity and selectivity.The catalytic system of [Ir(COD)Cl] 2 with an excess of the bulky phosphine P(o-MeOPh) 3 under transfer hydrogenation conditions of propan-2-ol and KOH was used successfully in the selective hydrogenation of cinnamaldehyde (Scheme 15.4) [4]. Selectivity and activity were found to increase with increasing P/Ir ratios, and complete conversion was achieved in as little as 5 minutes (turnover frequency (TOF) *6000 h -1 ). Hydrogenation of Aldehydes 415Scheme 15.2 Distribution of products in the hydrogenation of a,b-unsaturated aldehydes. Scheme 15.3 Hydrogenation of crotonaldehyde with [IrH 3 (PPh 3 ) 3 ] in acetic acid. Scheme 15.4 Transfer hydrogenation of cinnamaldehyde.Using molecular hydrogen as the reducing agent, [Ir(COD)(OCH 3 )] 2 with an excess of tertiary phosphine was better than [Ir(COD)Cl] 2 for the selective hydrogenation of cinnamaldehyde [5]. In these studies, a great dependence on solvent and ligand was reported. A variety of different phosphines, which were markedly different in their steric and electronic properties, were examined in this reaction. In propan-2-ol the most effective phosphine was PCy 2 Ph which gave 94% yield (TOF 235 h -1 ) of the unsaturated alcohol in a 2 h reaction under 30 bar H 2 at 100 8C. Phosphines such as PCyPh 2 , PPhPr i 2 , PPh 2 Pr i and PEtPh 2 were also effective in giving over 95% selectivity. The less-effective phosphines were PEt 2 Ph, PMePh 2 , PBu i 3 and PMe 2 Ph. Reactions that were performed in toluene were generally less effective.More recent advances in iridium-catalyzed aldehyde hydrogenation have been through the use of bidentate ligands [6]. In the hydrogenation of citral and cinnamaldehyde, replacing two triphenylphosphines in [IrH(CO)(PPh 3 ) 3 ] with bidentate phosphines BDNA, BDPX, BPPB, BISBI and PCP ( Fig. 15.1) led to an increase in catalytic activity. a) Selectivity of allylic alcohol formed as a percentage of total hydrogenation products. b) TOF (h -1 ) expressed for conversion of starting material. Hydrogenation of Aldehydes 419Scheme 15.5 Preparation of cationic DiPFc catalyst.

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Section: Cationic Rhodium Phosphine Catalystsmentioning

confidence: 97%

Section: Rh-amine Catalystsmentioning

confidence: 99%

Section: Reductive Amination Of Ketones and Aldehydesmentioning

confidence: 99%

Section: Reductive Amination Of Ketones and Aldehydesmentioning

confidence: 99%

See 2 more Smart Citations

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Clarke¹,

Roff²

2006

The Handbook of Homogeneous Hydrogenation

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“…The moderate yield of the compounds in this case was due to the easy evaporation of the low-boiling products under microwave irradiation. Surprisingly, cinnamaldehyde (entry 13), under the above conditions, provided dihydrocinnamyl alcohol and 4-methoxyphenylpropane [31] besides forming the expected dihydrocinnamaldehyde. Similarly, furan (entry 14) and coumarin (entry 15) produced tetrahydrofuran and phenylpropionic acid, respectively, along with the expected dihydro products.…”

Section: Full Papersmentioning

confidence: 95%

A Chemoselective Hydrogenation of the Olefinic Bond of α,β‐Unsaturated Carbonyl Compounds in Aqueous Medium under Microwave Irradiation

2006

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A microwave-assisted mild and ecofriendly catalytic transfer hydrogenation process was developed to reduce various a,b-unsaturated carbonyl compounds into the corresponding saturated carbonyl compounds in the presence of silica-supported palladium chloride as catalyst and a combination of MeOH/HCOOH/H 2 O (1 : 2 : 3) as hydrogen source within 22 -55 minutes in moderate to excellent yields with 100% chemoselectivity.

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Asymmetrische Katalyse mit hinsichtlich Struktur und Funktion gezielt entworfenen Molekülen: die chemo- und stereoselektive Hydrierung von Ketonen

2001

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Chemoselective Transfer Hydrogenation of α,β-Unsaturated Aldehydes to Allylic Alcohols Using Formic Acid Catalyzed by Polymer-Bound Rh Carbonyl Clusters

Cited by 46 publications

References 8 publications

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

A Chemoselective Hydrogenation of the Olefinic Bond of α,β‐Unsaturated Carbonyl Compounds in Aqueous Medium under Microwave Irradiation

Asymmetrische Katalyse mit hinsichtlich Struktur und Funktion gezielt entworfenen Molekülen: die chemo- und stereoselektive Hydrierung von Ketonen

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