Direct Hydrogenation of Carboxylic Acids to Corresponding Aldehydes Catalyzed by Palladium Complexes in the Presence of Pivalic Anhydride

Nagayama, Kazuhiro; Shimizu, Isao; Yamamoto, Akio

doi:10.1246/cl.1998.1143

Cited by 69 publications

(16 citation statements)

References 5 publications

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“…However, aldehyde productivity is limited to 50% by the reaction mechanism that involves hydrogenolysis of Pd-acyl and Pdcarboxylato groups in [Pd(PPh 3 ) 2 (C(O)R)(O 2 CR)] to give an equal mixture of aldehydes and acids [105]. Very bulky anhydrides were significantly more difficult to reduce, which led this group to design a process for converting carboxylic acids into aldehydes in the presence of bulky anhydrides [105][106][107]. Thus, heating a wide range of less sterically demanding acids in the presence of The reaction tolerates ketone, chloride, internal C=C bonds, esters, nitriles, and ether functional groups.…”

mentioning

confidence: 99%

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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confidence: 99%

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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“…46 We also noted that carboxylic anhydrides having relatively bulky substituents undergo the catalytic hydrogenation much more slowly than the less sterically hindered anhydrides. 46 We also noted that carboxylic anhydrides having relatively bulky substituents undergo the catalytic hydrogenation much more slowly than the less sterically hindered anhydrides.…”

Section: Equation 15mentioning

confidence: 72%

Chemistry of Monoorganopalladium Complexes Relevant to Catalysis

Yamamoto

Kayaki

Nagayama

et al. 2000

Synlett

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Neutral and cationic organopalladium complexes have been prepared as models for active intermediates involved in palladium-catalyzed reactions. Comparison of the reactivities of the neutral and cationic complexes revealed the much higher reactivities of the latter toward b-elimination and olefin or CO insertion. Generation of the solvent-coordinated hemilabile site on the cationic organopalladium complexes was indicated as a dominant factor in enhancing the reactivities. Utilizing the reactivity of an acylpalladium complex toward hydrogen, a novel, selective, and environmentally benign hydrogenation process catalyzed by palladium complexes to give various aldehydes has been developed.

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“…Through our studies on the comparative reactivities of various carboxylic anhydrides with Pd 0 complexes, we found that carboxylic anhydride such as 2,2dimethylpropionic anhydride (pivalic anhydride) proved to be much less reactive than the less-bulky carboxylic anhydrides [34] [35]. Prompted by this finding, we designed a catalytic system with pivalic anhydride added to the system containing the carboxylic acid to be hydrogenated.…”

Section: 2mentioning

confidence: 99%

Synthetic Design of Carbonyl-Group-Containing Compounds Based on C−O Bond Cleavage Promoted by Pd Complexes

Yamamoto

Kakino

Shimizu

2001

HCA

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Dedicated to Luigi M. Venanzi in memory of his outstanding scientific achievements On the basis of fundamental studies on elementary processes involving allylÀO and acylÀO bond cleavages, various new catalytic processes to convert carboxylic acid derivatives have been realized. The new processes include 1) carbonylation of allyl formates to b,g-unsaturated acids, 2) amination, alkylation, and carbonylation of allylic alcohols, 3) aldehyde synthesis by hydrogenation of carboxylic anhydrides and carboxylic acids, 4) ketone synthesis by combination of the CÀO bond cleavage with transmetallation by organoboronic acids. The processes described here have advantages over the conventional ones in that they are more atom-efficient and halogen-free in realizing the syntheses of a variety of carbonyl-containing compounds under mild conditions.

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Direct Hydrogenation of Carboxylic Acids to Corresponding Aldehydes Catalyzed by Palladium Complexes in the Presence of Pivalic Anhydride

Cited by 69 publications

References 5 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

Chemistry of Monoorganopalladium Complexes Relevant to Catalysis

Synthetic Design of Carbonyl-Group-Containing Compounds Based on C−O Bond Cleavage Promoted by Pd Complexes

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