A DFT study of the mechanism of palladium-catalyzed alkoxycarbonylation and aminocarbonylation of alkynes: Hydride versus amine pathways

Suleiman, Rami; Ibdah, Abdelletif; Ali, Bassam El

doi:10.1016/j.jorganchem.2011.02.027

Cited by 17 publications

(12 citation statements)

References 31 publications

(31 reference statements)

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“…Later on, El Ali and co-workers have proposed a reaction mechanism pathway based on DFT calculations for the aminocarbonylation of propyne. 236,237 Ionic liquid [bmin][Tf 2 N] has shown to be a good reaction medium for the synthesis of acrylamides from terminal aryl and alkyl acetylenes with primary and secondary amines. 238 Interestingly, no acidic cocatalyst was necessary [e.g., amine/ alkyne molar ratio 5:1, Pd(OAc) 2 (3 mol %), dppp (6 mol %), CO (14 atm), 110 °C, 22 h].…”

Section: Thioacidsmentioning

confidence: 99%

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Nonclassical Routes for Amide Bond Formation

2016

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The present review offers an overview of nonclassical (e.g., with no pre- or in situ activation of a carboxylic acid partner) approaches for the construction of amide bonds. The review aims to comprehensively discuss relevant work, which was mainly done in the field in the last 20 years. Organization of the data follows a subdivision according to substrate classes: catalytic direct formation of amides from carboxylic and amines ( section 2 ); the use of carboxylic acid surrogates ( section 3 ); and the use of amine surrogates ( section 4 ). The ligation strategies (NCL, Staudinger, KAHA, KATs, etc.) that could involve both carboxylic acid and amine surrogates are treated separately in section 5 .

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Section: Thioacidsmentioning

confidence: 99%

“…Later on, El Ali and co-workers have proposed a reaction mechanism pathway based on DFT calculations for the aminocarbonylation of propyne. , …”

Section: Carboxylic Acid Surrogatesmentioning

confidence: 99%

Nonclassical Routes for Amide Bond Formation

2016

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“…Suleiman et al performed DFT studies on Pd-diphosphine catalysed methoxycarbonylation of propyne at the B3LYP/6-31G*/LANL2DZ level of theory. 106 They discuss the branched to linear selectivity with 1,4-bis(phosphaneyl) butane ligand; however, the results appear rather inconclusive. For instance, the free energy profile shows the CO insertion as the highest overall barrier rather than the intramolecular methanolysis step, which contradicts all the computational studies discussed previously and subsequently.…”

Section: Palladium-catalysed Alkoxycarbonylation Of Alkynes With Chelating Phosphine Ligandsmentioning

confidence: 99%

Computational modelling of Pd-catalysed alkoxycarbonylation of alkenes and alkynes

Ahmad

Bühl

2021

Phys. Chem. Chem. Phys.

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“…Ali and co‐workers reported Pd(II)‐catalyzed aminocarbonylation and alkoxycarbonylation of terminal alkynes (Scheme and ) . The mechanisms of those two reactions have been studied by B3LYP functional calculation . As shown in Figure , the alkoxycarbonylation starts from the hydride Pd(II) species 100 , which can coordinate with an alkyne to form complex 102 .…”

Section: Mechanism Of Unsaturated Bond Transformationmentioning

confidence: 99%

On the Mechanism of Palladium‐Catalyzed Unsaturated Bond Transformations: A Review of Theoretical Studies

et al. 2019

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Palladium-catalyzed transformation reactions of unsaturated molecules have considerable importance because of their versatility and wide range of applications. Over the past decades, various experimental studies on palladiumcatalyzed unsaturated bond transformation have been reported, and mechanistic and computational studies have also progressed considerably. With the development of computing methods and power, theoretical calculation has become a powerful tool for mechanistic study of transition-metal catalysis. In this review, we summarize the literature on mechanistic studies of palladium-catalyzed transformations of unsaturated molecules, including hydrogenation, alkylation, arylation, silylation, vinylation, cyclization and esterification. Mechanistically, most of these reactions undergo a redox pathway, involving either oxidative addition, insertion, transmetalation, β-H elimination or reductive elimination. Some instead undergo a non-redox pathway, mainly involving insertion or β-H elimination.[a] Q. Scheme 1. The common redox mechanism of Pd catalyzed unsaturated bonds transformation. 2 3 4 5 6 7 8

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A DFT study of the mechanism of palladium-catalyzed alkoxycarbonylation and aminocarbonylation of alkynes: Hydride versus amine pathways

Cited by 17 publications

References 31 publications

Nonclassical Routes for Amide Bond Formation

Nonclassical Routes for Amide Bond Formation

Computational modelling of Pd-catalysed alkoxycarbonylation of alkenes and alkynes

On the Mechanism of Palladium‐Catalyzed Unsaturated Bond Transformations: A Review of Theoretical Studies

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