Glaser–Hay hetero-coupling in a bimetallic regime: a Ni(<scp>ii</scp>)/Ag(<scp>i</scp>) assisted base, ligand and additive free route to selective unsymmetrical 1,3-diynes

Mohanty, Anuradha; Roy, Sujit

doi:10.1039/c7cc05605b

Cited by 17 publications

(8 citation statements)

References 39 publications

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“…Increase of the ratio was helpful for the heterocoupling reaction, and when 1a / 2a was 5/1, yield of 3a reached 91% (entry 5). This observation is in a good accordance with the previous reports. − To ensure a good synthetic yield and also maximize the utilizing efficiency of substrate and the solvent for the product isolation, we continued the reactions with a ratio of 1a / 2a = 2/1. We suspected that, thanks to the formation of hydrogen bonds between alkynol and the solid support, alkynol component may be selectively enriched to some extent in the solid–liquid interface.…”

Section: Resultssupporting

confidence: 88%

Lignosulfonate/Dicationic Ionic Liquid Composite as a Task-Specific Catalyst Support for Enabling Efficient Synthesis of Unsymmetrical 1,3-Diynes with A Low Substrate Ratio

Lai

Bai

2018

ACS Sustainable Chem. Eng.

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In Glaser heterocoupling reactions, one of the alkyne precursors have to be used in five to ten times of excess. This not only wasted the organic substrate, but also decreased the catalytic efficiency of the metal catalysts. To solve this problem, we prepared a lignosulfonate/dicationic ionic liquid composite via ion exchange process. The thereby obtained materials can be used as catalyst supports for preparing heterogeneous Cu-based catalysts. The supports and the catalysts were characterized by many physicochemical methods including FT-IR, elemental analysis (EA), FSEM, FTEM, XPS, and TG. Interestingly, the catalyst can enrich the alkynol component in the reaction system, thus enabling Glaser heterocoupling reactions of alkynols and phenylacetylenes to proceed well with a low substrate ratio. The substrate scope of the Glaser heterocoupling reaction, enriching effect of the composite support for the alkynol component, and recyclability of the catalyst were also investigated.

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Section: Resultssupporting

confidence: 88%

Lignosulfonate/Dicationic Ionic Liquid Composite as a Task-Specific Catalyst Support for Enabling Efficient Synthesis of Unsymmetrical 1,3-Diynes with A Low Substrate Ratio

Lai

Bai

2018

ACS Sustainable Chem. Eng.

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“…The same group also reported the very first example of a Ni(II)/Ag(I)-catalyzed Glaser-Hay type cross-coupling reaction to produce unsymmetrical 1,3diynes. 75 The method is highly selective and works under mild and aerobic conditions without employing any base, ligand, or additives. In addition, a modified version of Cadiot− Chodkiewicz-type cross-coupling reaction was also reported recently to obtain unsymmetrical 1,3-diynes.…”

Section: Synthesismentioning

confidence: 99%

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

et al. 2018

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Conjugated poly-ynes and poly(metalla-ynes) constitute an important class of new materials with potential application in various domains of science. The key factors responsible for the diverse usage of these materials is their intriguing and tunable chemical and photophysical properties. This review highlights fascinating advances made in the field of conjugated organic poly-ynes and poly(metalla-ynes) incorporating group 4-11 metals. This includes several important aspects of conjugated poly-ynes viz. synthetic protocols, bonding, electronic structure, nature of luminescence, structure-property relationships, diverse applications, and concluding remarks. Furthermore, we delineated the future directions and challenges in this particular area of research.

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“…Recently, several protocols were established that display larger heteroselectivity and provide sufficient yields of the unsymmetrical diyne with application of the major alkyne in only two‐fold or even lower excess . Heterogeneous and homogeneous copper and gold catalysts as well as bimetallic Pd/Cu‐ and Ni/Ag‐based systems were successfully employed for these transformations. Propargylic and homopropargylic alcohols, ethers and esters are particularly useful substrates for these heterocouplings, since selective and subsequent alkyne activation is mediated by oxygen‐metal interaction …”

Section: Introductionmentioning

confidence: 99%

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

Schnabel

Melcher

Brandhorst

et al. 2018

Chemistry A European J

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The benzylidyne complex [PhC≡W{OSi(OtBu) } ] (1) catalyzed the cross-metathesis between 1,4-bis(trimethylsilyl)-1,3-butadiyne (2) and symmetrical 1,3-diynes (3) efficiently, which gave access to TMS-capped 1,3-diynes RC≡C-C≡CSiMe (4). Diyne cross-metathesis (DYCM) studies with C-labeled diyne PhC≡ C- C≡CPh (3*) revealed that this reaction proceeds through reversible carbon-carbon triple-bond cleavage and formation according to the conventional mechanism of alkyne metathesis. The reaction between 1 and 3* afforded the 3-phenylpropynylidyne complex PhC≡ C- C≡W{OSi(OtBu) } ] (5*), indicating that alkynylalkylidyne complexes are likely to act as catalytically active species. Attempts to isolate 5* from mixtures of 1 and 3* afforded crystals of the ditungsten 2-butyne-1,4-diylidyne complex [(tBuO) SiO} W≡ C- C≡ C- C≡W{OSi(OtBu) } ] (6*), which was additionally characterized by X-ray diffraction analysis. Depolymerization-macrocyclization of a carbazole-butadiyne polymer, obtained from 3,6-diethynyl-9-dodecylcarbazole (7) under copper-catalyzed Hay coupling conditions, was also efficiently catalyzed by 1 and afforded a mixture of mono-, diyne- and triyne-containing tetrameric macrocycles, revealing that diyne disproportionation into monoynes and triynes occurs as a slow side reaction that interferes with a high diyne metathesis selectivity. Potential catalytic pathways were studied by means of quantum-chemical calculations, and kinetic studies were performed to substantiate an α,α-mechanism for the catalytic diyne metathesis reaction, which involves intermediate alkynylalkylidyne and α,α'-dialkynylmetallacyclobutadiene intermediates.

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Glaser–Hay hetero-coupling in a bimetallic regime: a Ni(ii)/Ag(i) assisted base, ligand and additive free route to selective unsymmetrical 1,3-diynes

Abstract: A Ni(OAc)2/Ag(OTf) catalysed coupling of aryl alkynes and propargylic alcohol/ether/ester gave the corresponding unsymmetrical 1,3-diynes in good to excellent yields.

Cited by 17 publications

References 39 publications

Lignosulfonate/Dicationic Ionic Liquid Composite as a Task-Specific Catalyst Support for Enabling Efficient Synthesis of Unsymmetrical 1,3-Diynes with A Low Substrate Ratio

Lignosulfonate/Dicationic Ionic Liquid Composite as a Task-Specific Catalyst Support for Enabling Efficient Synthesis of Unsymmetrical 1,3-Diynes with A Low Substrate Ratio

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

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