Copper‐Catalyzed Sonogashira Reaction in Water

Liu, Yujia; Blanchard, Vincent; Danoun, Grégory; Zhang, Zhaoyang; Tlili, Anis; Zhang, Wenlong; Monnier, Florian; Lee, Arie Van Der; Mao, Jincheng; Taillefer, Marc

doi:10.1002/slct.201702854

Cited by 37 publications

(17 citation statements)

References 32 publications

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“…The current mechanistic understanding concerning copper(II) catalytic systems involves reduction of copper(II) to copper(I) by the solvent or the ligand (usually amines), followed by the mechanism proposed for copper(I) systems . The transient formation of yellow solids in the reaction mixture of copper‐catalyzed Sonogashira couplings has been attributed to intermediate copper acetylides . In the course of our experiments we observed that the reaction mixtures very often turned yellow, during the first minutes of the reaction, a fact we also believe is due to the transient formation of copper acetylides.…”

Section: Resultssupporting

confidence: 56%

A Sustainable, User‐Friendly Protocol for the Pd‐Free Sonogashira Coupling Reaction

et al. 2018

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We herein present a new catalytic system for the palladium‐free Sonogashira coupling reaction. The catalytically active moiety is formed in situ, in a straightforward and user‐friendly manner, by combining a widely available low‐cost copper salt and an N‐heterocyclic carbene precursor. A series of N‐heterocyclic carbene ligand precursors with variable structural features, some of which are novel, were tested and the reaction conditions were optimized. Using the catalytic system with the optimum performance, the scopes of the alkyne and the aryl halide were probed. Aryl iodides readily react with terminal alkynes, providing the coupling products in high to excellent yields. The protocol is highly efficient with alkynes bearing either alkyl or aryl substituents, the latter having either electron‐donating or electron‐withdrawing groups.

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Section: Resultssupporting

confidence: 56%

A Sustainable, User‐Friendly Protocol for the Pd‐Free Sonogashira Coupling Reaction

et al. 2018

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“…Based on the abovementioned observations, we suggested the most possible mechanistic pathway for this method. According to the results obtained from the control experiments as well as the literature, [10][11][12]37 under the same reaction conditions. No coupling products were found in the mixture.…”

Section: Mechanistic Studymentioning

confidence: 91%

The CuFe₂O₄@SiO₂@ZrO₂/SO₄²⁻/Cu nanoparticles: an efficient magnetically recyclable multifunctional Lewis/Brønsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water

et al. 2019

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“…However, these methods often require expensive Pd catalysts and Cu salts as cocatalyst with excessive ligands/amines or harsh thermal conditions. Recently, a number of reports have demonstrated different modifications in a catalytic fashion, such as a) Cu‐free Pd‐catalytic systems,– b) Pd‐free Fe‐, Ni‐, or Cu‐complexes, and c) Cu‐catalysts with ligands under harsh conditions . Among them, Pd‐free copper‐catalyzed Sonogashira cross‐couplings are the predominant inexpensive protocols for constructing conjugated alkynes, However, the usage of excess ligands and the harsh thermal reaction conditions diminish their merits.…”

Section: Methodsmentioning

confidence: 99%

Cu₂O Nanocrystals‐Catalyzed Photoredox Sonogashira Coupling of Terminal Alkynes and Arylhalides Enhanced by CO₂

et al. 2019

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Herein the first visible-light-activated Sonogashira CÀCc oupling reaction at room temperature catalyzed by single-metal heterogeneous Cu 2 Ot runcated nanocubes (Cu 2 OT NCs) was developed. Aw ide varietyo fa ryl halidesa nd terminal alkynes workedw ell in this recyclable heterogeneous photochemical process to form the corresponding Sonogashira CÀCc oupling products in good yields. Mechanistic control studies indicated that CO 2 enhances the formation of light-absorbing heterogeneous surface-bound Cu I -phenylacetylide (l max = 472 nm), which further undergoes single-electron transfer with aryl iodides/bromides to enable Sonogashira C sp 2ÀC sp bond formation. In contrastt ol iterature-reported bimetallic TiO 2 -containing nanoparticles as photocatalyst, this work avoided the need of cocatalysis by TiO 2 .S ingle-metalC u I in Cu 2 OT NCs wass olely responsible for the observed C sp 2ÀC sp couplingr eactions under CO 2 atmosphere.The Sonogashira coupling reactioniso ne of the most powerful and straightforwardm ethods forc onstruction of aryl alkynes/conjugated alkynes through C sp 2À C sp cross-coupling of aryl/alkenyl halidesa nd terminal alkynes, which are the most substantial intermediates in the synthesis of natural products as well as pharmaceutical, polymeric, and organic materials. [1] In such transformations, conventional methodologies involvet he use of palladiump hosphine complexes along with copper as ac ocatalyst in the presence of excess organic amine bases (Scheme 1a). [2] However, these methodso ften requiree xpensive Pd catalysts and Cu salts as cocatalyst with excessive ligands/ amines or harsh thermal conditions. Recently,a number of reports have demonstrated different modifications in ac atalytic fashion, [3] such as a) Cufree Pd-catalytic systems, [3a-d] b) Pd-free Fe-, Ni-, or Cu-complexes, [3e,f] and c) Cu-catalystsw ith ligandsu nder harsh conditions. [3g] Among them,P d-free copper-catalyzed Sonoga-shira cross-couplings are the predominant inexpensive protocols for constructing conjugated alkynes, [3d, 4, 5] However,t he usage of excessl igands and the harsh thermalr eaction conditions diminish their merits.To addresst he above challenges, we previously reported visible-light-triggered CuCl-catalyzed Sonogashira crosscoupling between aryl halides and terminal alkynes at room temperature. [6] We envisioned that the CÀCc oupling reactions can be initiated by photoexcited copper(I)-phenylacetylide that undergoes as ingle-electron transfer (SET) process with ground-state aryl halidesv ia inner-coordination sphere to initiate the CÀCc oupling reactionu pon visible-light irradiation. We questioned whether it is possible to replace the molecular CuCl catalystw ith recyclable solid copper-containing nanoparticles (NPs) for the Sonogashira C sp 2ÀC sp cross-coupling reactions between aryl halides and terminal alkynes under visiblelight irradiation at room temperature. Such recyclableh eterogeneous photocatalysts are highly desirable for Sonogashira coupling reactions and remainunexplored in th...

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Copper‐Catalyzed Sonogashira Reaction in Water

Abstract: International audienc

Cited by 37 publications

References 32 publications

A Sustainable, User‐Friendly Protocol for the Pd‐Free Sonogashira Coupling Reaction

A Sustainable, User‐Friendly Protocol for the Pd‐Free Sonogashira Coupling Reaction

The CuFe₂O₄@SiO₂@ZrO₂/SO₄²⁻/Cu nanoparticles: an efficient magnetically recyclable multifunctional Lewis/Brønsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water

Cu₂O Nanocrystals‐Catalyzed Photoredox Sonogashira Coupling of Terminal Alkynes and Arylhalides Enhanced by CO₂

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Copper‐Catalyzed Sonogashira Reaction in Water

Abstract: International audienc

Cited by 37 publications

References 32 publications

A Sustainable, User‐Friendly Protocol for the Pd‐Free Sonogashira Coupling Reaction

A Sustainable, User‐Friendly Protocol for the Pd‐Free Sonogashira Coupling Reaction

The CuFe2O4@SiO2@ZrO2/SO42−/Cu nanoparticles: an efficient magnetically recyclable multifunctional Lewis/Brønsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water

Cu2O Nanocrystals‐Catalyzed Photoredox Sonogashira Coupling of Terminal Alkynes and Arylhalides Enhanced by CO2

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The CuFe₂O₄@SiO₂@ZrO₂/SO₄²⁻/Cu nanoparticles: an efficient magnetically recyclable multifunctional Lewis/Brønsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water

Cu₂O Nanocrystals‐Catalyzed Photoredox Sonogashira Coupling of Terminal Alkynes and Arylhalides Enhanced by CO₂