Regiospecific N‐Arylation of Aliphatic Amines under Mild and Metal‐Free Reaction Conditions

Purkait, Nibadita; Kervefors, Gabriella; Linde, Erika; Olofsson, Berit

doi:10.1002/ange.201807001

Cited by 31 publications

(13 citation statements)

References 57 publications

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“…[27] Particularly important the direct arylation of various nucleophiles by diaryliodonium salts. Thus, the strong nucleophiles are able to react with electron-poor aryl electrophile without the addition of transition metals (for instance, amines, [28][29][30][31] alkoxides, [32][33][34] S-nucleophiles, [35,36] etc.). The weaker nucleophiles require higher temperatures or the addition of transition metals, especially…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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

et al. 2021

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“…Late-stage N-H arylation of indolines was then investigated by Natchsheim to design a streamlined and rapid synthetic route to the corresponding N -substituted compounds as key structures in organic electronics [ 89 , 90 ]. The reaction was extended to benzotriazole using t BuOK as a base, and the selective N2-arylation was observed in moderate yield using diaryliodonium triflates in propionitrile at 90 °C ( Scheme 19 ).…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Transition-Metal-Free Late-Stage C-H and N-H Arylation of Heteroarenes Using Diaryliodonium Salts

Besson

Fruit

2021

Pharmaceuticals

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Transition-metal-free direct arylation of C-H or N-H bonds is one of the key emerging methodologies that is currently attracting tremendous attention. Diaryliodonium salts serve as a stepping stone on the way to alternative environmentally friendly and straightforward pathways for the construction of C-C and C-heteroatom bonds. In this review, we emphasize the recent synthetic advances of late-stage C(sp2)-N and C(sp2)-C(sp2) bond-forming reactions under metal-free conditions using diaryliodonium salts as arylating reagent and its applications to the synthesis of new arylated bioactive heterocyclic compounds.

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“…[15][16][17] Modern approaches to the synthesis of diaryliodonium salts allow to prepare versatile scope of these compounds with high yields from common laboratory reagents. [18][19][20][21][22][23][24][25] Currently, diaryliodonium salts are widely used for arylation of N-nucleophiles, including amines, [26][27][28][29] amides, [30,31] and N-heterocycles [32][33][34][35][36][37][38] , etc. [39] Nevertheless, the chemoselectivity of arylation of N,O-containing heterocycles presents a challenging task in hypervalent iodine chemistry.…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Selective Arylation of Oxadiazolones by Diaryliodonium Salts

Soldatova¹,

Semenov²,

Geyl³

et al. 2021

Preprint

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The direct N-arylation of cyclic amides can be considered a pivotal issue for modern organic chemistry. Here, we report the method for copper-catalyzed N-arylation of diverse oxadiazolones by diaryliodonium salts in mild conditions in high yields (up to 92%) using available CuI as a catalyst. The developed method allows to efficiently utilize both symmetric and unsymmetric diaryliodonium salts bearing auxiliary groups such as 2,4,6-trimethoxyphenyl (TMP). The evaluation of steric effects in aryl moieties to the chemoselectivity of N- and O-arylation of the 1,2,4-oxadiazol-5(4H)-ones exhibited the high potential of mesityl-substituted diaryliodonium salts 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.

show abstract

Regiospecific N‐Arylation of Aliphatic Amines under Mild and Metal‐Free Reaction Conditions

Cited by 31 publications

References 57 publications

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

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

Recent Advances in Transition-Metal-Free Late-Stage C-H and N-H Arylation of Heteroarenes Using Diaryliodonium Salts

Copper-Catalyzed Selective Arylation of Oxadiazolones by Diaryliodonium Salts

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