Cu-catalyzed <i>N</i>-3-Arylation of Hydantoins Using Diaryliodonium Salts

Berntsen, Linn Neerbye; Nova, Ainara; Wragg, David S.; Sandtorv, Alexander H.

doi:10.1021/acs.orglett.0c00642

Cited by 16 publications

(25 citation statements)

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“…Based on experimental results and previous reports [24,42,46] we proposed the mechanism of the N‐ and N/O‐arylation of 1,2,4‐oxadiazol‐5‐ones (Scheme 4,a). Plausible mechanism includes the oxidative addition of CuI complex with Et 3 N to diaryliodonium salt following ligand exchange with deprotonated oxadiazolone and reductive elimination (Scheme 4,a).…”

Section: Resultsmentioning

confidence: 95%

“…Indeed, the current trends in the arylation of N-centered nucleophiles consume metal-free conditions, but the low nucleophilicity of 1 a did not favor the direct arylation (Table 1, Entries 1-4). In order to find suitable conditions, we added CuI as a cheap and available catalyst, which has been already applied for the arylation of hydantoins, [42] 2,7-naphthyridin-1(2H)one, [43] and other weak N-centered nucleophiles. [15,61] The addition of 10 mol % CuI in the presence of [a] Reaction conditions: 1 a (0.5 mmol), 2 a (0.75 mmol), of 2 a, base (0.75 mmol) in 5 mL of solvent for 24 h in Ar.…”

Section: Resultsmentioning

confidence: 99%

“…The electron-rich heterocycles can be arylated by iodonium salts in relatively mild conditions, [37][38][39][40] while electron-poor (especially cyclic amides and related compounds) require the addition of catalyst. [41][42][43][44][45][46] Also, the synthetic procedures for preparing diaryliodonium salts make available the versatile scope of these compounds with high yields from common laboratory reagents. [47][48][49][50][51][52][53][54] Nevertheless, the chemoselectivity of arylation of N,O-containing heterocycles presents a challenging task in hypervalent iodine chemistry.…”

Section: Research Articlementioning

confidence: 99%

“…The decrease of yield is in agreement with the behavior of sterically hindered diaryliodonium salt 2 f and reported data about arylation of Nnucleophiles with TMP-substituted iodonium salts. [37,39,42] To our delight, the reaction's scope could be extended to 1,3,4-oxadiazol-2(3H)-ones 5 (Scheme 6, a). The published approaches to arylation of 1,3,4oxadiazol-2(3H)-ones limited only to corresponding 5alkyl-derivatives prepared by interaction with haloar-Table 2.…”

Section: Research Article Ascwiley-vchdementioning

confidence: 99%

“…The particular interest has been appealed by the N‐arylation of heterocycles. The electron‐rich heterocycles can be arylated by iodonium salts in relatively mild conditions, [37–40] while electron‐poor (especially cyclic amides and related compounds) require the addition of catalyst [41–46] . Also, the synthetic procedures for preparing diaryliodonium salts make available the versatile scope of these compounds with high yields from common laboratory reagents [47–54] …”

Section: Introductionmentioning

confidence: 99%

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Copper‐Catalyzed Selective N‐Arylation of Oxadiazolones by Diaryliodonium Salts

et al. 2021

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Here, we report the method for copper-catalyzed N-arylation of diverse oxadiazolones by diaryliodonium salts under mild conditions in high yields (up to 92%) using available CuI as a catalyst. The developed method allows utilizing both symmetric and unsymmetric diaryliodonium salts bearing auxiliary groups such as 2,4,6-trimethoxyphenyl (TMP). We found that the steric effects in aryl moieties determined the chemoselectivity of N-and O-arylation of the 1,2,4-oxadiazol-5(4H)-ones. Mesityl-substituted diaryliodonium salts demonstrated the high potential as a selective arylation reagent. The structural study suggests that steric accessibility of N-atom in 1,2,4-oxadiazol-5(4H)-ones impact to arylation with sterically hindered diaryliodonium salts. The synthetic application of proposed method was also demonstrated on selective arylation of 1,3,4-oxadiazol-2(3H)-ones and 1,2,4-oxadiazole-5-thiol.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Research Articlementioning

confidence: 99%

Section: Research Article Ascwiley-vchdementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Copper‐Catalyzed Selective N‐Arylation of Oxadiazolones by Diaryliodonium Salts

et al. 2021

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Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

et al. 2022

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This review outlines the progress over recent years in the reactions involving combined approach of hypervalent iodine reagents and transition metals such as palladium, nickel, iridium, gold, rhodium, copper, iron, ruthenium, platinum, silver, zinc, rhenium and cobalt. This approach enables organic transformations complimentary to traditional manifolds. Hypervalent iodine reagents play a preeminent role in organic chemistry due to their versatile reactivity, heteroatom ligands and mild reaction conditions. These reagents in combination of transition metal compounds are used in many synthetically useful organic reactions such as oxidation, rearrangement, amination, halogenation, amidation, ring-opening, cyclization and CÀ H and CÀ C functionalization reactions, etc. which are discussed here. Combination with Cobalt 2.3. Reactions of Hypervalent Iodine Reagents with Copper 2.4. Reactions of Hypervalent Iodine Reagents in Combination with Nickel 2.5. Reactions of Hypervalent Iodine Reagents in Combination with Zinc 3. Transformations Involving Hypervalent Iodine Reagents and 2 nd Transition Series Metals 3.1. Reactions of Hypervalent Iodine Reagents in Combination with Ruthenium 3.2. Reactions of Hypervalent Iodine Reagents in Combination With Rhodium 3.3. Reactions of Hypervalent Iodine Reagent in Combination With Palladium 3.4. Reactions of Hypervalent Iodine Reagents in Combination with Silver 4. Transformations Involving Hypervalent Iodine Reagents and 3rd Transition Series Metals 4.1. Reactions of Hypervalent Iodine Reagents in Combination with Rhenium 4.2. Reactions of Hypervalent Iodine Reagents in Combination with Iridium 4.3. Reactions of Hypervalent Iodine Reagents in Combination with Platinum 4.4. Reactions of Hypervalent Iodine Reagents in Combination with Gold 5. Conclusion

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A Mechanistic Study of the Cu‐catalyzed N‐arylation of Hydantoin with Aryl(TMP)iodonium Salts

Neerbye Berntsen,

Nova

2023

ChemCatChem

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The use of diaryliodonium salts in organic reactions has rapidly increased in the last decade because of their efficiency in arylation reactions. Despite this, mechanistic investigations are still scarce, particularly for copper catalyzed N‐arylation reactions. Recently, we published the use of the unsymmetrical aryl(TMP)iodonium salts (TMP = 2,4,6‐trimethoxyphenyl) for the selective Cu‐catalyzed N‐arylation of hydantoins. In this work, the mechanism of this reaction has been studied by DFT methods, and our results have been compared with previous and new experimental data. In contrast to the mechanism proposed for C‐H arylation reactions, our results suggest that deprotonation of hydantoin precedes the oxidative addition of aryl(TMP)iodonium salt, with the oxidative addition to a Cu(I) imido intermediate and ligand rearrangements being the rate‐limiting steps. This mechanism agrees with the species observed by NMR spectroscopy, kinetic isotope experiments, and the product yields observed using aryl(TMP)iodonium salts with different steric and electronic properties. In addition, it gives some hints for increasing the efficiency of arylation reactions by tuning the diaryliodonium salt.

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Cu-catalyzed N-3-Arylation of Hydantoins Using Diaryliodonium Salts

Cited by 16 publications

References 59 publications

Copper‐Catalyzed Selective N‐Arylation of Oxadiazolones by Diaryliodonium Salts

Copper‐Catalyzed Selective N‐Arylation of Oxadiazolones by Diaryliodonium Salts

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

A Mechanistic Study of the Cu‐catalyzed N‐arylation of Hydantoin with Aryl(TMP)iodonium Salts

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