Sustainable route to biomass-based amines: rhodium catalyzed hydroaminomethylation in green solvents

Dias, Adelson de O.; Gutiérrez, María G.P.; Avendaño-Villarreal, Jesus A.; Carmo, Raul L.L.; Oliveira, Kelley C.B.; Santos, Alexandra G.; Santos, Eduardo N. dos; Gusevskaya, Elena V.

doi:10.1016/j.apcata.2019.02.003

Cited by 13 publications

(4 citation statements)

References 35 publications

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“…However, the economic viability of such reaction on an industrial scale is compromised by the high price of the rhodium catalyst and utilization of phosphines. [3][4][5] Effective recyclability and low catalyst loading are thus required. To prevent utilization of phosphines, alternatives emerged such as Rh/amine combinations.…”

Section: Introductionmentioning

confidence: 99%

“…These tandem reactions occur under CO/H 2 pressure in a one‐pot procedure, which is very appealing from a synthetic viewpoint. However, the economic viability of such reaction on an industrial scale is compromised by the high price of the rhodium catalyst and utilization of phosphines . Effective recyclability and low catalyst loading are thus required.…”

Section: Introductionmentioning

confidence: 99%

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Selective Ruthenium‐Catalyzed Hydroaminomethylation of Unsaturated Oleochemicals

Cousin

Hapiot

Monflier

2019

Euro J Lipid Sci & Tech

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Rhodium-catalyzed hydroaminomethylation (HAM) is recently described as an innovative way to functionalize triglycerides. In the search to reduce production costs, rhodium is sought to be replaced by ruthenium whose price is currently more than 20 times lower. In this study, HAM of unsaturated oleochemicals using ruthenium precursors is proceeded under phosphine-free conditions. The experimental conditions are optimized by changing the nature of the solvent, the reaction temperature, and the CO/H 2 pressure. While rhodium leads to good catalytic activity and low chemoselectivity (mixture of hydroxyl and amino groups), ruthenium proves to be less active but more chemoselective as amino-substituted products are mainly formed. Of interest, HAM of methyl 10-undecenoate (MU) occurs in a highly chemo-and regioselective fashion using acetonitrile as solvent. Practical Applications: Selective Ru-catalyzed hydroaminomethylation can be implemented on an industrial scale for the conversion of unsaturated oleochemicals into amines. This finding is of importance as the obtained amino-products can be used in many industrial areas such as surfactants, polymers, or lubricants.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Selective Ruthenium‐Catalyzed Hydroaminomethylation of Unsaturated Oleochemicals

Cousin

Hapiot

Monflier

2019

Euro J Lipid Sci & Tech

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“…[53] The reaction was performed with di-n-butylamine (i) as a condensation counterpart under the conditions optimized for the HAM of 2-propenylbenzenes in our related study. [54] Two isomers of amine 8 ai were obtained in 87 % selectivity at a nearly complete substrate conversion, with the regioselectivity for the desired branched isomer being 69 % (iso/n ratio of 69/31). The rest of the mass balance was due to unreacted enamines 7 ai and small amounts of alcohols 6 a.…”

Section: Resultsmentioning

confidence: 99%

“…The additional catalyst, [Rh 2 (μ‐OMe) 2 (COD) 2 ] (Figure 2), was employed in this run as we have previously found that the ruthenium catalyst, M73SIPr, is not active in hydroformylation after being used in ethenolysis [53] . The reaction was performed with di‐ n ‐butylamine ( i ) as a condensation counterpart under the conditions optimized for the HAM of 2‐propenylbenzenes in our related study [54] . Two isomers of amine 8 ai were obtained in 87 % selectivity at a nearly complete substrate conversion, with the regioselectivity for the desired branched isomer being 69 % (iso/n ratio of 69/31).…”

Section: Resultsmentioning

confidence: 99%

2‐Arylpropylamines from 1‐Propenylbenzenes in a New One‐Pot Metathesis–Hydroaminomethylation Protocol

et al. 2023

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2-Arylpropylamines are useful as active pharmaceutical ingredients (APIs) and as synthetic building blocks in fine chemistry. Herein we report a new and efficient methodology to transform naturally occurring 1-propenylbenzenes into 2-arylpropylamines employing a one-pot ethenolysis/hydroaminomethylation protocol. Four consecutive reactions must occur in the same reaction vessel and the careful selection of the reaction conditions was critical to obtain the desired products in high yields. The negative interference between the ethenolysis and the hydroaminomethylation (HAM) catalysts was circumvented by the appropriate adjustment on the molar ratio of the catalysts. As a result, nine 2-arylpropylamines were obtained in yields ranging in 75-93 %.

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Rhodium‐Catalyzed Carbonylations

Piccolo¹,

Paganelli

2021

Carbon Monoxide in Organic Synthesis

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Sustainable route to biomass-based amines: rhodium catalyzed hydroaminomethylation in green solvents

Cited by 13 publications

References 35 publications

Selective Ruthenium‐Catalyzed Hydroaminomethylation of Unsaturated Oleochemicals

Selective Ruthenium‐Catalyzed Hydroaminomethylation of Unsaturated Oleochemicals

2‐Arylpropylamines from 1‐Propenylbenzenes in a New One‐Pot Metathesis–Hydroaminomethylation Protocol

Rhodium‐Catalyzed Carbonylations

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