N¹‐ and N³‐Arylations of Hydantoins Employing Diaryliodonium Salts via Copper(I) Catalysis at Room Temperature

Abstract

Dedicated to Prof. Viktor V. Zhdankin for his outstanding contribution to Hypervalent Iodine Chemistry. Copper(I)-catalyzed N-arylation (both N 1-and N 3-) of hydantoins with diaryliodonium salts as aryl partners at room temperature is reported. The transformation allows diverse scopes on both hydantoins and diaryliodonium salts delivering functionalized N 3-arylated products under mild reaction conditions. The presence of hydrogens at C 5-and N 1-position of the hydantoin does not lead to other side products. Chiral hydantoins can also be synthesized via this methodology. Sterically complicated ortho-substituted diaryliodonium salts are tolerated and delivered challenging ortho-arylated products. In addition, this strategy can also be effectively extended to N 1-arylation of hydantoins.

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

“…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.…”

“…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] …”

Ligand-free Ullmann-type arylation of oxazolidinones by diaryliodonium salts

“…For this reason, copper-based catalysts have proven to be versatile. 13 For example, copper-catalyzed arylations with diaryliodonium salts have been described for naphthalimides, 23 hydantoins, 24,25 naphthyridinone, 26 phthalhydrazides, 27 and oxadiazolones. 28 However, the conditions for these arylations are highly dependent on the type of electron-deficient azaheterocycles, so that for each type of heterocycles, complete optimization and tuning of the conditions is required.…”

Ligand-Free Ullmann-Type Arylation of Oxazolidinones by Diaryliodonium Salts

“…For this reason, copper-based catalysts have proven to be versatile. 21 For example, copper-catalyzed arylations with diaryliodonium salts has been described for naphthalimides, 28 hydantoins, 29,30 naphthyridinone, 31 phthalhydrazides, 32 and oxadiazolones. 33 However, the conditions for these arylations are highly dependent on the type of electron-deficient azaheterocycles, so that for each type of heterocycles, complete optimization and tuning of the conditions is required.…”