Highly efficient synthesis of unsymmetrical 1,3-diynes from organoalane reagents and alkynyl bromides mediated by a nickel catalyst

Mo, Song; Shao, Xuebei; Zhang, Gang; Li, Qinghan

doi:10.1039/c7ra02758c

Cited by 21 publications

(7 citation statements)

References 74 publications

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“…The isolated yield of 4 a (88 %) is larger than the yield determined by NMR spectroscopy for a 4:1 mixture of 2 and 3 a (80 %, see Table ), which we ascribe to the error of the NMR experiment and to the different reaction conditions. Overall, our new method for the preparation of TMS‐capped 1,3‐butadiynes is clearly able to compete with alternative procedures employing, among others, Cadiot–Chodkiewicz‐ or Sonogashira‐type coupling reactions …”

Section: Resultsmentioning

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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Section: Resultsmentioning

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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“…However, a minor amount (2-5 %) of homocoupled products was also generated which can be easily removed during the purification process. Using the same procedure biologically relevant conjugated 1,3-enynes 102 can also be synthesized in impressive yields by the CspÀ Csp 2 crosscoupling of alkynyl bromides and alkenyl boronic acids. [103] The reaction proceededwith complete retention of stereochemistry,thus,the coupling of (E)-styrenylwith vinyl boronic acids gave the (E)-1,3-enynes.…”

Section: Synthesis Of Unsymmetric 13-diynes and Conjugated 13-enynesmentioning

confidence: 99%

“…The conjugated 1,3-diynes are useful building blocks in pharmaceuticals, polymers, natural products, industrial and optical materials. [102] The group of Ranu described the applications of commercially available CuFe 2 O 4 nanoparticle as a catalyst for unsymmetric1,3-diynes synthesisin the presence of dimethyl carbonate (DMC) as a green reaction medium andCs 2 CO 3 as base. [103] The CspÀ Csp cross-coupling of a series of diversely substituted (alkyl, cycloalkyl, aryl, and heteroaryl) alkynyl bromides with various substituted alkynyl boronic esters provided a library of unsymmetric 1,3-diynesin high yields.…”

Section: Synthesis Of Unsymmetric 13-diynes and Conjugated 13-enynesmentioning

confidence: 99%

Synthesis and Reactivity of Copper and Copper Containing Magnetically Separable Catalysts

Kundu

Mondal

Das³

et al. 2022

ChemistrySelect

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This review endeavours to summarize the emergence of magnetically separable catalysts as a new class of catalyst for the modern developments in the synthesis and reactivity of the nano‐sized magnetically separable copper and copper containing nanomaterials exploited as potent applicant in the field of material science not only for their widespread technological applications but also to realize the fundamentals of nano‐magnetism. This review covers extensively different catalytic reactivity for carbon‐carbon and carbon‐heteroatom bond formation reactions and emphasized on recent developments in the field.

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“…Dimethylalkynylaluminum reagents can also react with alkynyl bromides in the presence of nickel(0) catalysts to generate unsymmetrical diynes in good yields (Scheme 27). 51…”

Section: Scheme 26 Palladium-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

Synthesis and Reactivity of Mixed Dimethylalkynylaluminum Reagents

Piccardi¹,

Turcaud²,

Benedetti³

et al. 2018

Synthesis

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Organoaluminum derivatives are mostly appreciated for their Lewis acidity properties, but generally not considered as reagents of choice in synthetic transformations involving the creation of C–C bonds. Among these species, dimethylalkynylaluminum reagents represent a special class of compounds, with, in many cases, unique reactivity. This review summarizes the preparation and reactivity of these organometallic reagents with a focus on their synthetic potential.1 Introduction2 Preparation of Dimethylalkynylaluminum Reagents3 Reactivity of Dimethylalkynylaluminum Reagents3.1 Reactions with Csp3 Electrophiles3.2 Reactions with Csp2 Electrophiles4 Transition-Metal-Catalyzed Reactions4.1 Addition to α,β-Unsaturated Enones4.2 Coupling Reactions5 Triple Bond Reactivity6 Conclusion

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Highly efficient synthesis of unsymmetrical 1,3-diynes from organoalane reagents and alkynyl bromides mediated by a nickel catalyst

Abstract: Highly efficient and simple cross-coupling reactions of alkynylbromides with organoalane reagents for the synthesis of unsymmetrical 1,3-diynes derivatives using Ni(OAc)2 (2–5 mol%)/(o-furyl)3P (4–10 mol%) as a catalyst are reported.

Cited by 21 publications

References 74 publications

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

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

Synthesis and Reactivity of Copper and Copper Containing Magnetically Separable Catalysts

Synthesis and Reactivity of Mixed Dimethylalkynylaluminum Reagents

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