Efficient alkyne homocoupling catalysed by copper immobilized on functionalized silica

Gelderen, Laurens van; Rothenberg, Gadi; Calderone, V. Roberto; Wilson, Karen; Shiju, N. Raveendran

doi:10.1002/aoc.2933

Cited by 29 publications

(17 citation statements)

References 42 publications

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“…8 With respect to catalysis by metals, Van Gelderen et al showed that silica-4 supported Cu was effective 9 as were ligand-stabilized Cu clusters. 10 Most recently, Boronat et al…”

Section: Introductionmentioning

confidence: 99%

Critical Role of Oxygen in Silver-Catalyzed Glaser–Hay Coupling on Ag(100) under Vacuum and in Solution on Ag Particles

et al. 2017

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The essential role of oxygen in enabling heterogeneously catalyzed Glaser−Hay coupling of phenylacetylene on Ag(100) was elucidated by STM, laboratory and synchrotron photoemission, and DFT calculations. In the absence of coadsorbed oxygen, phenylacetylene formed well-ordered dense overlayers which, with increasing temperature, desorbed without reaction. In striking contrast, even at 120 K, the presence of oxygen led to immediate and complete disruption of the organic layer due to abstraction of acetylenic hydrogen with formation of a disordered mixed layer containing immobile adsorbed phenylacetylide. At higher temperatures phenylacetylide underwent Glaser−Hay coupling to form highly ordered domains of diphenyldiacetylene that eventually desorbed without decomposition, leaving the bare metal surface. DFT calculations showed that, while acetylenic H abstraction was otherwise an endothermic process, oxygen adatoms triggered a reaction-initiating exothermic pathway leading to OH(a) + phenylacetylide, consistent with the experimental observations. Moreover, it was found that, with a solution of phenylacetylene in nonane and in the presence of O 2 , Ag particles catalyzed Glaser−Hay coupling with high selectivity. Rigorous exclusion of oxygen from the reactor strongly suppressed the catalytic reaction. Interestingly, too much oxygen lowers the selectivity toward diphenyldiacetylene. Thus, vacuum studies and theoretical calculations revealed the key role of oxygen in the reaction mechanism, subsequently borne out by catalytic studies with Ag particles that confirmed the presence of oxygen as a necessary and sufficient condition for the coupling reaction to occur. The direct relevance of model studies to a mechanistic understanding of coupling reactions under conditions of practical catalysis was reaffirmed.

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“…8 With respect to catalysis by metals, Van Gelderen et al showed that silica-4 supported Cu was effective 9 as were ligand-stabilized Cu clusters. 10 Most recently, Boronat et al…”

Section: Introductionmentioning

confidence: 99%

Critical Role of Oxygen in Silver-Catalyzed Glaser–Hay Coupling on Ag(100) under Vacuum and in Solution on Ag Particles

et al. 2017

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“…In order to show the merits and limitations of the present work in comparison with other reported catalytic systems in the literatures, we summarized some of results for the synthesis of 1,2‐diphenylethyne via homo‐coupling of phenylacetylene in Table . As can be seen in this table, the present catalytic system is an equally or more efficient to those previously reported in this reaction, since the use of precious metal catalyst, [12, 15,] high reaction temperature, or the employment of unrecyclable catalysts can be avoided.…”

Section: Resultsmentioning

confidence: 58%

“…Various catalytic systems have been developed for this reaction using O 2 or air as the oxidant, including the use of Cu, Pd, Ag, Au and bimetallic Pd/Cu, Pd/Ag and Fe/Cu . Some heterogeneous catalysts, like silica/chitosan core–shell hybrid‐microsphere‐supported CuI, copper nanoparticles supported on silica coated maghemite, copper immobilized on functionalized silica, polymer‐supported copper, Cu(I) immobilized on functionalized SBA‐15, immobilized copper in MCM‐41, mesoporous silica‐supported copper, copper immobilized on nano‐silica triazine dendrimer, copper‐impregnated magnetite have also been successfully employed to promote this reaction. In 2016, Sheng et al reported that copper porphyrin acted as an efficient catalyst with high TON .…”

Section: Introductionmentioning

confidence: 99%

Magnetic copper ferrite catalyzed homo‐ and cross‐coupling reaction of terminal alkynes under ambient atmosphere

Wang

Zhao

et al. 2017

Applied Organom Chemis

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The application of non-toxic and magnetically separable nano-CuFe 2 O 4 as an efficient catalyst for oxidative homo-and cross-coupling reaction of terminal alkynes is described. A wide range of symmetrical and unsymmetrical 1,3-diynes have been synthesized in moderate to good yields under ambient atmosphere. The nano CuFe 2 O 4 can be recovered with a magnet and reused at least five consecutive cycles with no appreciable loss of its catalytic activity.

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“…Especially, the uses of copper FS catalysts in coupling reactions are widespread. Copper(I) FS catalysts are efficiently utilized in A 3 coupling, Glaser‐Hay coupling and Sonogashira coupling reactions . Furthermore, copper(0) FS and copper(II) FS are the efficient catalysts in A 3 coupling and C−N coupling reactions, respectively.…”

Section: Applications and Advantages Of Fs‐based Catalystsmentioning

confidence: 99%

Functionalized Silicas for Metal‐Free and Metal‐Based Catalytic Applications: A Review in Perspective of Green Chemistry

Antony

Marimuthu

Yang

et al. 2019

The Chemical Record

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Heterogeneous catalysis plays a key role in promoting green chemistry through many routes. The functionalizable reactive silanols highlight silica as a beguiling support for the preparation of heterogeneous catalysts. Metal active sites anchored on functionalized silica (FS) usually demonstrate the better dispersion and stability due to their firm chemical interaction with FSs. Having certain functional groups in structure, FSs can act as the useful catalysts for few organic reactions even without the need of metal active sites which are termed as the covetous reusable organocatalysts. Magnetic FSs have laid the platform where the effortless recovery of catalysts is realized just using an external magnet, resulting in the simplified reaction procedure. Using FSs of multiple functional groups, we can envisage the shortened reaction pathway and, reduced chemical uses and chemical wastes. Unstable bio‐molecules like enzymes have been stabilized when they get chemically anchored on FSs. The resultant solid bio‐catalysts exhibited very good reusability in many catalytic reactions. Getting provoked from the green chemistry aspects and benefits of FS‐based catalysts, we confer the recent literature and progress focusing on the significance of FSs in heterogeneous catalysis. This review covers the preparative methods, types and catalytic applications of FSs. A special emphasis is given to the metal‐free FS catalysts, multiple FS‐based catalysts and magnetic FSs. Through this review, we presume that the contribution of FSs to green chemistry can be well understood. The future perspective of FSs and the improvements still required for implementing FS‐based catalysts in practical applications have been narrated at the end of this review.

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Efficient alkyne homocoupling catalysed by copper immobilized on functionalized silica

Cited by 29 publications

References 42 publications

Critical Role of Oxygen in Silver-Catalyzed Glaser–Hay Coupling on Ag(100) under Vacuum and in Solution on Ag Particles

Critical Role of Oxygen in Silver-Catalyzed Glaser–Hay Coupling on Ag(100) under Vacuum and in Solution on Ag Particles

Magnetic copper ferrite catalyzed homo‐ and cross‐coupling reaction of terminal alkynes under ambient atmosphere

Functionalized Silicas for Metal‐Free and Metal‐Based Catalytic Applications: A Review in Perspective of Green Chemistry

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