Copper‐Catalyzed Arylation of Nucleophiles by Using Butadienylphosphines as Ligands: Mechanistic Insight

Kaddouri, Hamid; Vicente, Virginie; Ouali, Armelle; Ouazzani, Fouad; Taillefer, Marc

doi:10.1002/anie.200800688

Cited by 106 publications

(39 citation statements)

References 34 publications

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“…In a previous report dealing with the Cu‐catalyzed coupling of aryl halides with nitrogen heterocycles and phenols by using butadienylphosphines ligand, we were able, following the reaction with 31 P NMR spectroscopy, to get crucial information on the reaction pathway and the catalytic cycle involved. We tried to apply a similar strategy to study the mechanism of the copper catalyzed Sonogashira reaction and selected very simple phosphorus ligands (PPh 3 ), associated to CuI as precatalyst.…”

Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Sonogashira Reaction in Water

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Sonogashira Reaction in Water

et al. 2017

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“…[25] This step is generally exothermic by 40.2 kcal/mol (Int3a-1→CuOH), 65.7 kcal/mol (Int4b-1→HOCuNMP), 71.8 kcal/mol (Int4b-2→BrCuNMP), and 63.5 kcal/mol (Int4a-1→ HOCuNH 3 ). In Pathway A', moderately endothermic reductive elimination reaction is also observed with 15.5 kcal/mol (Int3a-2→CuBr), which is slightly thermodynamically unfavorable for the production of the final target compound (PhNH 2 ).…”

Section: Reductive Elimination Reactionmentioning

confidence: 99%

A Theoretical Insight into the Mechanism of Cu(I)‐Catalyzed CN Coupling between Aryl Halides and Aqueous Ammonia

et al. 2015

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Computational investigations of Cu(I)-catalyzed C-N coupling between aryl halides and aqueous ammonia without addition of any base or ligand were reported. Density functional theory calculations were performed to reveal the mechanism of the ligand-free amination reaction for the preparation of primary aromatic amines. Through systematic evaluation of the relative concentrations of possible Cu species in solution, we propose that the active catalyst is the neutral Cu(I) complexes rather than the Cu(I) cations; oxidative addition of aryl bromide is a facile step of the catalytic cycle; reactant (NH 3 ) and solvent molecule (NMP) can act as ligands of Cu species to help reduce the activation energy of the forward reaction and increase the activation energy of the reverse reaction; except for Pathway B, the deprotonation step is irreversible due to the extreme exothermic feature; the elimination of H 2 O is kinetically favored, while that of HBr is thermodynamically preferred. These findings should be valuable for the mechanism understandings of the ligand-free Cu-catalyzed C-N cross-coupling reactions and for the further development of highly efficient amination catalyst systems.

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“…2–5 Indeed, vinyl aryl ethers constitute useful intermediates in a wide range of reactions; for example, cycloadditions, cyclopropanations, metathesis reactions, natural product analogues, and polymers. 2 N-Vinyl amines are widely used in the preparation of polymeric dyes, catalysts and ion-exchange resins, while the vinyl group can also act as an efficient protecting group of phenol derivatives.…”

Section: Introductionmentioning

confidence: 99%

Base-Mediated Stereospecific Synthesis of Aryloxy and Amino Substituted Ethyl Acrylates

et al. 2011

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The stereospecific synthesis of aryloxy and amino substituted E- and Z-ethyl-3-acrylates is of interest because of their potential in the polymer industry and in medicinal chemistry. During work on a copper-catalyzed cross-coupling reaction of E- and Z-ethyl-3-iodo-acrylates with phenols and N-heterocycles, we discovered a very simple (non-metallic) method for the stereospecific synthesis of aryloxy and amino substituted acrylates. To study this long standing problem on the stereoselectivity of aryloxy and amino substituted acrylates, a series of O- and N-substituted nucleophiles was allowed to react with E- and Z-ethyl-3-iodo-acrylates. Screening of different bases indicated that DABCO (1,4-diazabicyclo[2.2.2]octane) afforded successful conversion of E- and Z- ethyl-3-iodoacrylates into aryloxy and amino substituted ethyl acrylates in a stereospecific manner. Herein are the details of this DABCO-mediated stereospecific synthesis of aryloxy and amino substituted E- or Z-acrylates.

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Copper‐Catalyzed Arylation of Nucleophiles by Using Butadienylphosphines as Ligands: Mechanistic Insight

Abstract: International audienc

Cited by 106 publications

References 34 publications

Copper‐Catalyzed Sonogashira Reaction in Water

Copper‐Catalyzed Sonogashira Reaction in Water

A Theoretical Insight into the Mechanism of Cu(I)‐Catalyzed CN Coupling between Aryl Halides and Aqueous Ammonia

Base-Mediated Stereospecific Synthesis of Aryloxy and Amino Substituted Ethyl Acrylates

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