The First Efficient Hydroaminomethylation with Ammonia: With Dual Metal Catalysts and Two-Phase Catalysis to Primary Amines

Zimmermann, Burkhard; Herwig, Jürgen; Beller, Matthias

doi:10.1002/(sici)1521-3773(19990816)38:16<2372::aid-anie2372>3.0.co;2-h

Cited by 197 publications

(64 citation statements)

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“…[19] Hydroaminomethylation using a dual metal catalyst system was investigated for the first time by Beller et al [20] Using propene, butene and pentene as an olefin they achieved the formation of primary amines in an aqueous two-phase process and the hydrogenation of imines could be improved.…”

Section: Figurementioning

confidence: 99%

Cascade Reactions in Polymeric Nanoreactors: Mono (Rh)‐ and Bimetallic (Rh/Ir) Micellar Catalysis in the Hydroaminomethylation of 1‐Octene

Gall

Bortenschlager

Nuyken

et al. 2008

Macro Chemistry & Physics

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The concept of micellar catalysis was transferred to the hydroaminomethylation of 1‐octene with N,N‐dimethylamine. In the first series of experiments a rhodium(I) complex with amphiphilic triphenylphosphane functionalized poly(2‐oxazoline)s as macroligand was applied as catalyst. Results obtained under standard hydroformylation conditions (T = 100 °C, p = 50 bar) were not satisfying with regard to activities and selectivities of the hydroaminomethylation reaction. Rising the temperature to 150 °C increased the yield of amine to 22% with a corresponding n/iso selectivity of 7.5 and a TOF number of 461 h−1. Best results were obtained by applying a dual Rh/Ir catalyst within the polymeric micelles leading at lower temperature of 130 °C to an amine yield of 24% with a corresponding n/iso selectivity of 11 and TOF numbers of about 600 h−1.magnified image

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Section: Figurementioning

confidence: 99%

Cascade Reactions in Polymeric Nanoreactors: Mono (Rh)‐ and Bimetallic (Rh/Ir) Micellar Catalysis in the Hydroaminomethylation of 1‐Octene

Gall

Bortenschlager

Nuyken

et al. 2008

Macro Chemistry & Physics

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“…The first example of hydroaminomethylation was reported as early as 1943 [83]. The most synthetically useful procedures utilize rhodium [84][85][86][87], ruthenium [88], or dual-metal (Rh/Ir) catalysts [87,89,90]. This area was reviewed extensively by one of the leading research groups in 1999 [91], and so is only briefly outlined here as the second step in the domino process is reductive amination of aldehydes.…”

Section: Hydroaminomethylation Of Alkenes (Domino Hydroformylation-rementioning

confidence: 99%

“…Running the reaction with excess alkene allows for secondary amines to be synthesized with excellent chemo-and regioselectivity. The catalyst displays up to 4000 turnovers with respect to rhodium, although relatively high concentrations of phosphine ligand seem to be required [90].…”

Section: Hydroaminomethylation Of Alkenes (Domino Hydroformylation-rementioning

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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“…Examples include the aminations of olefins and alkynes [16][17][18][19][20][21][22][23], catalytic hydroaminomethylations [24][25][26][27][28][29][30], and more recently amination of alcohols as well as amines [31][32][33][34][35][36][37][38]. Our work on the development of novel catalytic reductions to give amines started around 2007 when we got interested in the ruthenium-catalyzed hydrogenation of nitriles.…”

Section: Resultsmentioning

confidence: 99%

Selective Catalytic Reductions of Amides and Nitriles to Amines

et al. 2010

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The First Efficient Hydroaminomethylation with Ammonia: With Dual Metal Catalysts and Two-Phase Catalysis to Primary Amines

Abstract: Primary and unbranched secondary amines are obtained by the highly selective hydroaminomethylation of olefins with ammonia [Eq. (a)]. The selectivity is readily controlled with a new dual Rh/Ir catalyst in a two-phase system.

Cited by 197 publications

References 2 publications

Cascade Reactions in Polymeric Nanoreactors: Mono (Rh)‐ and Bimetallic (Rh/Ir) Micellar Catalysis in the Hydroaminomethylation of 1‐Octene

Cascade Reactions in Polymeric Nanoreactors: Mono (Rh)‐ and Bimetallic (Rh/Ir) Micellar Catalysis in the Hydroaminomethylation of 1‐Octene

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

Selective Catalytic Reductions of Amides and Nitriles to Amines

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