Diverse reactivity of carbenes and silylenes towards fluoropyridines

Kundu, Gargi; Ajithkumar, V. S.; Bisai, Milan Kumar; Tothadi, Srinu; Das, Tamal; Vanka, Kumar; Sen, Sakya S.

doi:10.1039/d1cc01401c

Cited by 9 publications

(7 citation statements)

References 35 publications

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“…However, even after repeated attempts, we were unable to stop this hydrolysis and hence, could not characterize 5a spectroscopically. The CF 3 group of the triflate moiety in 5b resonates at −78.6 ppm in the 19 F NMR, which is slightly different from the resonances of triflates bound to the boron atom (−76.7 ppm in 4) and is characteristic of the free triflate anion.…”

Section: Resultsmentioning

confidence: 85%

“…Clearly, the extension of unexplored carbenes in NHC•borane chemistry is desirable, as it may lead to the discovery of a range of interesting new applications. Due to our current interest in 5-SIDipp [17][18][19], we have prepared here haloboranes 5SIDipp•BHCl 2 , 1 and 5SIDipp•BPhCl 2 , 2 and studied their substitution reactions with AgOTf, AgNO 3 , and water. Furthermore, we have shown that the combination 5-SIDipp and B(C 6 F 5 ) 3 led to the activation of THF and diethyl ether via frustrated Lewis pair (FLP) way.…”

Section: Introductionmentioning

confidence: 99%

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Nucleophilic Substitution at a Coordinatively Saturated Five-Membered NHC∙Haloborane Centre

2022

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In this paper, we have used a saturated five-membered N-Heterocyclic carbene (5SIDipp = 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidine) for the synthesis of SNHC-haloboranes adducts and their further nucleophilic substitutions to put unusual functional groups at the central boron atom. The reaction of 5-SIDipp with RBCl2 yields Lewis-base adducts, 5-SIDipp·RBCl2 [R = H (1), Ph (2)]. The hydrolysis of 1 gives the NHC stabilized boric acid, 5-SIDipp·B(OH)3 (3), selectively. Replacement of chlorine atoms from 1 and 2 with one equivalent of AgOTf led to the formation of 5-SIDipp·HBCl(OTf) (4) and 5-SIDipp·PhBCl(OTf) (5a), where all the substituents on the boron atoms are different. The addition of two equivalents of AgNO3 to 2 leads to the formation of rare di-nitro substituted 5-SIDipp·BPh(NO3)2 (6). Further, the reaction of 5-SIDipp with B(C6F5)3 in tetrahydrofuran and diethyl ether shows a frustrated Lewis pair type small molecule activated products, 7 and 8.

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Section: Resultsmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Nucleophilic Substitution at a Coordinatively Saturated Five-Membered NHC∙Haloborane Centre

2022

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“…The smooth formation of 5 and 6 encouraged us to exploit the fluoride affinity of the silicon atoms in the hypersilyl moiety. In line with our current interest in C–F bond activation of perfluoroarenes, − we assume that the reactions of 3 or 4 with perfluoroarene might cleave the C–F bond of the fluoroarene and generate organo-germanium or tin compounds along with the elimination of (Me 3 Si) 3 SiF. Alternatively, the tetrylene center can undergo oxidative addition .…”

Section: Resultsmentioning

confidence: 88%

Access to a Variety of Ge(II) and Sn(II) Compounds through Substitution of Hypersilyl Moiety

et al. 2021

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We have prepared amidinato-germylene (3) and -stannylene (4) with a tris(trimethylsilyl)silyl substituent and subsequently substituted the hypersilyl moiety by reacting 3 with chlorophosphines, which led to phosphino germylenes (5 and 6) with concomitant liberation of (Me 3 Si) 3 SiCl. Exploiting the fluoride affinity of the silicon atom, we have prepared pentafluoropyridyl germylene (7) and -stannylene (8) by reacting 3 and 4 with C 5 F 5 N with simultaneous elimination of (Me 3 Si) 3 SiF. These are the first examples of aryl germylenes or stannylenes prepared via C−F bond activation of a perfluoroarene. The reaction of 4 with Me 3 NO resulted in a novel Sn 2 O 2 ring (9). All compounds were characterized by single-crystal X-ray structure determination studies.

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“…Sen group also theoretically calculated the ▵G for the triple C−F activation and characterized the complex by single X‐ray spectroscopy (Scheme 36). [82] …”

Section: C−f Bond Activation By N‐heterocyclic Carbene and Their Isoe...mentioning

confidence: 99%

C−F Bond Activation and Functionalizations Enabled by Metal‐free NHCs and Their Metal Complexes

Muthuvel

Gandhi

2022

ChemCatChem

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The activation and functionalization of CÀ F bonds in various fluoroorganics were found to be a daunting task owing to their innate inertness. Harnessing the CÀ F bonds will alleviate the toxicity and environmental issues posed by them, and provide new pathways to access value-added products. Although several strategies have been employed such as metal complexes, Brønsted acids, Lewis acids, and photocatalyst to activate the CÀ F bonds, however, the use of NHC or Metal-NHC is relatively scarce. NHCs based catalytic CÀ F activation stands out owing to its easy accessibility, stability, and facile reactivity. Metal-NHCs were exploited in hydrodefluorination, CÀ C, and CÀ B coupling reactions. Additionally, RÀ M(F)(NHC), an oxidative-addition intermediate that was conveniently isolated allows to decode catalytic CÀ F functionalization pathways. This minireview provides the prominence of NHC and metal-NHC in the area of catalytic CÀ F bond functionalization.

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Diverse reactivity of carbenes and silylenes towards fluoropyridines

Abstract: The reaction of IDipp with C5F5N led to functionalization of all three carbon atoms of the imidazole ring with HF2-as the counter-anion (1). Reactivity with 2,3,5,6-tetrafluoropyridine gives only C−F bond...

Cited by 9 publications

References 35 publications

Nucleophilic Substitution at a Coordinatively Saturated Five-Membered NHC∙Haloborane Centre

Nucleophilic Substitution at a Coordinatively Saturated Five-Membered NHC∙Haloborane Centre

Access to a Variety of Ge(II) and Sn(II) Compounds through Substitution of Hypersilyl Moiety

C−F Bond Activation and Functionalizations Enabled by Metal‐free NHCs and Their Metal Complexes

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