Phosphine‐ and Hydrogen‐Free: Highly Regioselective Ruthenium‐Catalyzed Hydroaminomethylation of Olefins

Gülak, Samet; Wu, Lipeng; Liu, Qiang; Franke, Robert; Jackstell, Ralf; Beller, Matthias

doi:10.1002/anie.201402368

Cited by 48 publications

(34 citation statements)

References 47 publications

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“…Current research deals with the application of the water‐gas shift or reversed water‐gas shift reaction using carbon monoxide and water or carbon dioxide and hydrogen in the hydroaminomethylation instead of syngas . Eilbracht et al has done research on hydroaminomethylation in synthesizing dendrimers .…”

Section: Introductionmentioning

confidence: 99%

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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This article describes the development of an effective thermomorphic multicomponent solvent (TMS) system for the production of branched polyamide monomers. In this system, methyl oleate, a renewable from fats and oils, and a functionalized amine are used as starting materials in a tandem catalytic reaction, which merges different reaction steps into a single preparative step. This particular TMS system consisted of a heptane/acetonitrile solvent mixture and made reusing the precious rhodium catalyst possible in three recycle runs. A constant yield of 61–65% was obtained for each run due to low‐catalyst leaching. Fortunately, the catalyst system does not require any additional phosphorous ligands and allows high yields. A scale‐up for the production of 10–11 g of the desired product in each run was realized. Subsequent hydrogenation of the product directly provided an amine ester, which is a valuable polyamide monomer. Practical applications: A method was developed to enable access to primary amines via hydroaminomethylation and hydrogenation. The product, a nitrile ester, is a valuable intermediate for polyamide monomers. This nitrile ester was successfully hydrogenated to an amine ester, which features a potential polyamide monomer directly. A catalyst recycle of the homogeneous rhodium complex within the hydroaminomethylation of methyl oleate and an amino nitrile was successfully carried out, enabling constant homogeneous catalyst activity over the course of three recycle runs. A scale‐up to obtain 10–11 g of the hydroaminomethylation product was realized. A general method is described for the conversion of methyl oleate within a hydroaminomethylation reaction. The catalyst can be recovered and reused. Valuable polyamide intermediates were obtained.

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Section: Introductionmentioning

confidence: 99%

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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“…Various olefins and aromatic aldehydes underwent efficient transformation in the presence of a cooperative rhodium/phosphine and organocatalyst system to afford the corresponding a,b-unsaturated aldehydes in good to excellent yields with high E stereoselectivities. [25] Our synthetic protocol is straightforward, atom-efficient, and does not need stoichiometric amounts of additives or base. Key to success is Table 4.…”

Section: Resultsmentioning

confidence: 99%

“…[a] Entry Solvent Conversion [%] [b] Yield [%] 5 aa (E/Z) [c] Yield [%] 3 a (E/Z) [c] the inherently low concentration of the aldehyde formed in the hydroformylation step. [25] Our synthetic protocol is straightforward, atom-efficient, and does not need stoichiometric amounts of additives or base. Because of the importance of a,b-unsaturated aldehydes in bulk and fine chemical industries, we believe this practical synthetic strategy has the potential to be used frequently.…”

Section: Resultsmentioning

confidence: 99%

Domino‐Hydroformylation/Aldol Condensation Catalysis: Highly Selective Synthesis of α,β‐Unsaturated Aldehydes from Olefins

Fang

Jackstell

Franke

et al. 2014

Chemistry A European J

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A general and highly chemo-, regio-, and stereoselective synthesis of α,β-unsaturated aldehydes by a domino hydroformylation/aldol condensation reaction has been developed. A variety of olefins and aromatic aldehydes were efficiently converted into various substituted α,β-unsaturated aldehydes in good to excellent yields in the presence of a rhodium phosphine/acid-base catalyst system. In view of the easy availability of the substrates, the high atom-efficiency, the excellent selectivity, and the mild conditions, this method is expected to complement current methodologies for the preparation of α,β-unsaturated aldehydes.

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“…Using ac ombination of Ru 3 (CO) 12 and K 2 CO 3 ,t he hydroaminomethylation reaction proceeds cleanly with aw ide range of olefins and primary/secondary amines (Figure 12 a). [174] Remarkably,t he site-selectivity for the linear product is high (typically > 95:5) even in the absence of ligands.U nder these conditions,t he catalyst displays selectivity for terminal olefins,w hereas internal olefins are unreactive.However,inamodified approach, which employs ap hosphinoimidazole ligand, internal olefins become reactive and undergo isomerization to furnish the linear amine product when possible (Figure 12 b). [175]…”

Section: Hydroaminomethylationmentioning

confidence: 99%

Harnessing the Power of the Water‐Gas Shift Reaction for Organic Synthesis

Ambrosi

Denmark

2016

Angew Chem Int Ed

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Since its original discovery over a century ago, the water-gas shift reaction (WGSR) has played a crucial role in industrial chemistry, providing a source of H2 to feed fundamental industrial transformations such as the Haber–Bosch synthesis of ammonia. Although the production of hydrogen remains nowadays the major application of the WGSR, the advent of homogeneous catalysis in the 1970s marked the beginning of a synergy between WGSR and organic chemistry. Thus, the reducing power provided by the CO/H2O couple has been exploited in the synthesis of fine chemicals; not only hydrogenation-type reactions, but also catalytic processes that require a reductive step for the turnover of the catalytic cycle. Despite the potential and unique features of the WGSR, its applications in organic synthesis remain largely underdeveloped. The topic will be critically reviewed herein, with the expectation that an increased awareness may stimulate new, creative work in the area.

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Phosphine‐ and Hydrogen‐Free: Highly Regioselective Ruthenium‐Catalyzed Hydroaminomethylation of Olefins

Cited by 48 publications

References 47 publications

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Domino‐Hydroformylation/Aldol Condensation Catalysis: Highly Selective Synthesis of α,β‐Unsaturated Aldehydes from Olefins

Harnessing the Power of the Water‐Gas Shift Reaction for Organic Synthesis

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