Transition‐metal‐catalyzed dehydrogenative coupling of alcohols and amines: A novel and atom‐economical access to amides

Heravi, Mohammad Reza Poor; Hosseinian, Akram; Rahmani, Zahra; Ebadi, Abdol Ghaffar; Vessally, Esmail

doi:10.1002/jccs.202000301

Cited by 27 publications

(4 citation statements)

References 100 publications

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“…Reactions based on catalytic dehydrogenative coupling are green and atom-economic routes for the synthesis of organic compounds. , Several carbonyl compounds such as ketones, esters, and amides, along with polymers such as polyesters, and polyamides, , can be synthesized using the approach of acceptorless catalytic dehydrogenative coupling of alcohols and amines. − This approach has also been utilized for the synthesis of urea derivatives via the dehydrogenative coupling of amines and methanol. The first example of the synthesis of urea derivatives from the dehydrogenative coupling of amines and methanol was reported by Hong using a ruthenium-Macho-BH pincer catalyst ( A , Figure ).…”

Section: Introductionmentioning

confidence: 99%

Manganese-Catalyzed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

et al. 2022

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Urea derivatives have significant applications in the synthesis of resin precursors, dyes, agrochemicals, and pharmaceutical drugs. Furthermore, polyureas are useful plastics with applications in coating, adhesive, and biomedical industries. However, the conventional methods for the synthesis of urea derivatives and polyureas involve toxic reagents such as (di)isocyanates, phosgene, CO, and azides. We present here the synthesis of (poly)ureas using much less toxic reagents(di)amines and methanolvia a catalytic dehydrogenative coupling process. The reaction is catalyzed by a pincer complex of an earthabundant metal, manganese, and liberates H 2 gas, valuable by itself, as the only byproduct, making the overall process highly atomeconomic. A broad variety of symmetrical and unsymmetrical urea derivatives and polyureas have been synthesized in moderate to quantitative yields using this catalytic protocol. Mechanistic insights have also been provided using experiments and DFT computation, suggesting that the reaction proceeds via an isocyanate intermediate.

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Section: Introductionmentioning

confidence: 99%

Manganese-Catalyzed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

et al. 2022

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“…The distortion of the NH 3 fragment still makes no difference in the two pathways. For the acylpalladium fragment, the related distortion energies (ΔE dis 3 and ΔE dis 4 ) are significantly larger than those with P( t Bu) 3 (ΔE dis 1 and ΔE dis 2 ) because the squareplanar acylpalladium 31 and 35 distorted to square-planar 7. Optimized structures and NPA charges of key aminolysis transition states (left) and energy-decomposition analysis (right).…”

Section: Resultsmentioning

confidence: 90%

“…In recent research studies, increasing attention has been focused on atom-economical synthetic methodologies with readily available materials as they provide green and sustainable access to value-added chemicals. In this context, amide synthesis from more stable carbon/oxygen resources such as alcohols, aldehydes, ketones, water, and hydrocarbons, has been developed. Among the various strategies, transition-metal-catalyzed hydroaminocarbonylation (HAC) of alkenes with CO and amines represents one of the most economical methods .…”

Section: Introductionmentioning

confidence: 99%

Double-Regiodetermining-Stages Mechanistic Model Explaining the Regioselectivity of Pd-Catalyzed Hydroaminocarbonylation of Alkenes with Carbon Monoxide and Ammonium Chloride

Liu

et al. 2021

J. Org. Chem.

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Pd-catalyzed hydroaminocarbonylation (HAC) of alkenes with CO and NH 4 Cl enables atom-economic and regiodivergent synthesis of primary amides, but the origin of regioselectivity was incorrectly interpreted in previous computational studies. A density functional theory study was performed herein to investigate the mechanism. Different from the previous proposals, both alkene insertion and aminolysis were found to be potential regioselectivity-determining stages. In the alkene insertion stage, 2,1insertion is generally faster than 1,2-insertion irrespective of neutral or cationic pathways for both P( t Bu) 3 and xantphos. Such selectivity results from the unconventional proton-like hydrogen of the Pd−H bond in alkene insertion transition states. For less bulky alkenes, aminolysis with P( t Bu) 3 shows low selectivity, while linear selectivity dominates in this stage with xantphos due to a stronger repulsion between xantphos and branched acyl ligands. It was further revealed that the less-mentioned CO concentration and solvents also influence the regioselectivity by adjusting the relative feasibilities of CO-involved steps and NH 3 release from ammonium chloride, respectively. The presented double-regiodeterminingstages mechanistic model associated with the effects of ligands, CO concentration, and solvents well reproduced the experimental selectivity to prove its validity and illuminated new perspectives for the regioselectivity control of HAC reactions.

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“…17,18 Several carbonyl compounds such as ketones, esters, and amides, along with polymers such as polyesters, 19 and polyamides 20,21 can be synthesized using the approach of acceptorless catalytic dehydrogenative coupling of alcohols and amines. [22][23][24][25] This approach has also been utilized for the synthesis of urea derivatives via the dehydrogenative coupling of amines and methanol. The first example of the synthesis of urea derivatives from the dehydrogenative coupling of amines and methanol was reported by Hong using a ruthenium-Macho-BH pincer catalyst (A, Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Manganese Catalysed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

Owen

Preiss

McLuskie

et al. 2021

Preprint

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Urea derivatives are prevalent intermediates in the synthesis of resin precursors, dyes, agrochemicals, and pharmaceutical drugs. Furthermore, polyureas are useful plastics with applications in coating, adhesive, and biomedical industries and have a current annual market of USD 885 million. However, the conventional methods for the synthesis of urea derivatives and polyureas involve toxic reagents such as (di)isocyanates, phosgene, CO, and azides. We present here the synthesis of (poly)ureas using much less toxic reagents - (di)amines, and methanol via a catalytic dehydrogenative coupling process. The reaction is catalyzed by a pincer complex of an earth-abundant metal, manganese, and liberates H2 gas, valuable by itself, as the only by-product making the overall process atom-economic, and sustainable. A broad variety of symmetrical, and unsymmetrical urea derivatives and polyureas have been synthesized in moderate to quantitative yields using this catalytic protocol. Mechanistic insights have also been provided using experiments and DFT computation suggesting that the reaction proceeds via an isocyanate intermediate.

show abstract

Transition‐metal‐catalyzed dehydrogenative coupling of alcohols and amines: A novel and atom‐economical access to amides

Cited by 27 publications

References 100 publications

Manganese-Catalyzed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

Manganese-Catalyzed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

Double-Regiodetermining-Stages Mechanistic Model Explaining the Regioselectivity of Pd-Catalyzed Hydroaminocarbonylation of Alkenes with Carbon Monoxide and Ammonium Chloride

Manganese Catalysed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

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