Labile dioxy-functionalised zwitterionic imidazolinium salt: access to zwitterionic and neutral imidazolidin-2-ylidene derivatives and π-acceptor properties of imidazolidine-2-selones

Gupta, Vivek; Karthik, Vedhagiri; Anantharaman, Ganapathi

doi:10.1039/c5ra15333f

Cited by 12 publications

(2 citation statements)

References 70 publications

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“… Known strategies (A and B) and new strategy developed in this study (C) to access 4(5)‐heteroatom‐functionalized imidazol(in)ium salts. In the known strategies, typical reagents containing preinstalled heteroatomic substituents include: i ) bielectrophiles such as α‐halogenoacetic [13a,c, 18a–e] or propiolic acid derivatives, [18f,g] α‐halogenated ketones, [18h] derivatives of oxalic acid, [18i,j] and 1,2‐dihalogen(or diphosphonio)‐1,2‐diaminoethenes; [13a, 18k] ii ) binucleophiles such as (thio)amides of aminoacetic acid; [18l,m] and iii ) oxazolinium salts [18n] …”

Section: Introductionmentioning

confidence: 99%

One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts

et al. 2022

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Imidazolium salts have ubiquitous applications in energy research, catalysis, materials and medicinal sciences. Here, we report a new strategy for the synthesis of diverse heteroatom‐functionalized imidazolium and imidazolinium salts from easily available 1,4‐diaza‐1,3‐butadienes in one step. The strategy relies on a discovered family of unprecedented nucleophilic addition/cyclization reactions with trialkyl orthoformates and heteroatomic nucleophiles. To probe general areas of application, synthesized N‐heterocyclic carbene (NHC) precursors were feasible for direct metallation to give functionalized M/carbene complexes (M=Pd, Ni, Cu, Ag, Au), which were isolated in individual form. The utility of the chloromethyl function for the postmodification of the synthesized salts and Pd/carbene complexes was demonstrated. The obtained complexes and imidazolium salts demonstrated good activities in Pd‐ or Ni‐catalyzed model cross‐coupling and C−H activation reactions.

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Section: Introductionmentioning

confidence: 99%

One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts

et al. 2022

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“…One of the recently suggested and introduced modifications of carbenes is the addition of a positive or negative charge to NHCs. Anionic NHCs (Figure a) were obtained both in the isolated form and in metal complexes, − and in the latter systems, they were shown to possess, in general, good stability because of their high affinity for transition metals bearing a formal positive charge . Surprisingly, however, there is not a single example of any of the anionic NHC derivatives complexing Ru to form a potential metathesis catalyst, although such systems have been proposed in computational studies and predicted to be stable and good candidates for efficient metathesis catalysts. , The cationic NHCs (Figure b) were also reported, − and it was shown that the positive charge on the NHC affects the electron properties by reducing the σ-donation properties and slightly increasing the π-acidity.…”

Section: Introductionmentioning

confidence: 99%

Impact of the Carbene Derivative Charge on the Decomposition Rates of Hoveyda–Grubbs-like Metathesis Catalysts

et al. 2020

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Hoveyda–Grubbs metathesis catalysts undergo a relatively fast decomposition in the presence of olefins. Using a computational density functional theory approach, we show that positively charged derivatives of N-heterocyclic carbenes have little impact on the degradation/deactivation rates of such catalysts with respect to neutral carbenes. On the other hand, the hypothetical anionic Hoveyda–Grubbs-like catalysts are predicted to less likely undergo degradation in the presence of the olefin, while being as active as standard, neutral Hoveyda–Grubbs catalysts.

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One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts

et al. 2022

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Imidazolium salts have ubiquitous applications in energy research, catalysis, materials and medicinal sciences. Here, we report a new strategy for the synthesis of diverse heteroatom-functionalized imidazolium and imidazolinium salts from easily available 1,4-diaza-1,3-butadienes in one step. The strategy relies on a discovered family of unprecedented nucleophilic addition/cyclization reactions with trialkyl orthoformates and heteroatomic nucleophiles. To probe general areas of application, synthesized N-heterocyclic carbene (NHC) precursors were feasible for direct metallation to give functionalized M/carbene complexes (M = Pd, Ni, Cu, Ag, Au), which were isolated in individual form. The utility of the chloromethyl function for the postmodification of the synthesized salts and Pd/carbene complexes was demonstrated. The obtained complexes and imidazolium salts demonstrated good activities in Pd-or Ni-catalyzed model cross-coupling and CÀ H activation reactions.

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Labile dioxy-functionalised zwitterionic imidazolinium salt: access to zwitterionic and neutral imidazolidin-2-ylidene derivatives and π-acceptor properties of imidazolidine-2-selones

Abstract: The synthesis of the title compound and effect of backbone oxy-derivatisation in imidazolidine derivatives on the π-acceptor property are reported.

Cited by 12 publications

References 70 publications

One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts

One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts

Impact of the Carbene Derivative Charge on the Decomposition Rates of Hoveyda–Grubbs-like Metathesis Catalysts

One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts

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