A New General Preparation of Polyfunctional Diarylamines by the Addition of Functionalized Arylmagnesium Compounds to Nitroarenes

Sapountzis, Ioannis; Knöchel, Paul

doi:10.1021/ja026718r

Cited by 143 publications

(87 citation statements)

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“…Among numerous methods to prepare diarylamines, the use of metallic catalysts, especially Pd2(dba)3 and Pd(OAc)2, is one of the most attractive routes. [3][4][5][6][7][8][9][10] These metals catalyze the reaction only in the form of metal-organic complexes, which constitute the active catalysts in many C-N bond formation cross-coupling methodologies for the synthesis of diarylamines, while such complexes are quite difficult to prepare and extremely air sensitive. 11 Although the reactions can sometimes be catalyzed by diverse ligands, the different kind and concentration of ligands may lead to various products.…”

Section: Introductionmentioning

confidence: 99%

Smiles rearrangement for the synthesis of diarylamines

Tian¹,

Wu²,

Li³

et al. 2011

Arkivoc

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Section: Introductionmentioning

confidence: 99%

Smiles rearrangement for the synthesis of diarylamines

Tian¹,

Wu²,

Li³

et al. 2011

Arkivoc

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“…Knochel and co-workers 83 described a procedure for the preparation of polyfunctionalized diarylamines by the reaction of arylmagnesium reagents with nitroarenes (Scheme 18). In this procedure not only organomagnesium reagent but also nitroarene can bear either electronwithdrawing or electron-donating groups.…”

Section: Scheme 17mentioning

confidence: 99%

Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

Daşkapan

2011

Arkivoc

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“…A functionalized arylamino functionality can be introduced into the heteroaryl compounds by reaction of nitro-substituted heterocycles with functionalized arylmagnesium species followed by reductive work-up procedure. 27 Thus, the reaction of 4-iodophenylmagnesium chloride with 6-nitrobenzothiazole (76) leads under usual conditions to the desired arylated amine 77 in 64% yield respectively (Scheme 12). 27 Similarly, the reaction of nitroquinoline 78 with arylmagnesium compound 79 furnishes the 6-(arylamino)quinoline 80 in 59% yield (Scheme 12).…”

Section: Preparation Of Heterocycles With Sensitive Functionalities Vmentioning

confidence: 99%

“…27 Thus, the reaction of 4-iodophenylmagnesium chloride with 6-nitrobenzothiazole (76) leads under usual conditions to the desired arylated amine 77 in 64% yield respectively (Scheme 12). 27 Similarly, the reaction of nitroquinoline 78 with arylmagnesium compound 79 furnishes the 6-(arylamino)quinoline 80 in 59% yield (Scheme 12). 27 Alternatively, an arylamino functionality can be introduced by the reaction of a functionalized heteroarylmagnesium reagent such as indolylmagnesium reagent 82 with highly electrophilic arylazotosylate such as 83 (Scheme 13).…”

Section: Preparation Of Heterocycles With Sensitive Functionalities Vmentioning

confidence: 99%

Preparation and Reactions of Heteroaryl Organomagnesium Compounds

Ila¹,

Baron²,

Wagner³

et al. 2005

Chemistry Letters

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The halogen/magnesium-exchange reaction has opened new perspectives in organic synthesis and has considerably extended the range of available functionalized aryl and heteroaryl magnesium compounds bearing functional groups such as ester, nitrile, iodide, imine, or even sensitive groups like nitro, hydroxy, and boronic esters. The present review summarizes the applications of these functionalized heteroaryl-and arylmagnesium compounds for the synthesis of a wide variety of regiospecifically functionalized five-and six-membered heterocycles. Ç 1. IntroductionThe selective functionalization of heteroaryl compounds is an important synthetic task. The resulting polyfunctional heteroaryl derivatives are often essential building blocks in the synthesis of natural products, 1 drugs, 2 new materials with defined properties, 3 or for the use in molecular recognition. 4 Although, directed metallation 5 or selective bromine/lithium-exchange 6 has provided a way to prepare a range of lithiated heterocycles, the high polarity of the carbon-lithium bond precludes the presence of sensitive functional groups such as ester and cyano groups in these lithium organometallics due to their too high reactivity. On the other hand, the more covalent character of the carbon-magnesium bond tolerates the presence of more functional groups. The synthesis of these polyfunctional Grignard reagents is, however, a problem, since the insertion of magnesium metal to aryl or heteroaryl halides bearing electron-withdrawing groups is inhibited by the presence of these functionalities. 7 Recently, we have shown that the halogen/magnesium-exchange reaction is a unique method for the preparation of a range of new functionalized aryl, alkenyl, and heteroaryl magnesium compounds, which has considerably extended the range of functionalized Grignard reagents available for synthetic purposes. These functionalized organomagnesium compounds have an excellent reactivity towards a wide range of electrophiles and they readily undergo transmetallation to provide a wide variety of organometallic reagents, particularly organocopper reagents which react especially well with soft electrophiles and display an excellent chemoselectivity. In the present review, we wish to report applications of this halogen/magnesium-exchange reactions for the preparation of a wide range of functionalized heteroaryl Grignard reagents and their reactions, which provide an entry to numerous polyfunctional five and six membered heterocyles. Ç 2. Synthesis of Functionalized Heterocycles Using Functionalized Heterocyclic Grignard ReagentsA variety of functionalized heterocyclic Grignard reagents can be prepared by using an I/Mg-or Br/Mg-exchange reaction.8 It was found earlier that aryl and heteroaryl iodides bearing electron-withdrawing groups undergo an I/Mg-exchange between À30 and À20C within a few hours, 8 and this exchange was applicable to a variety of heteroaryl iodides. The Br/Mgexchange 8 can also be applied to various heterocycles with electron-withdrawing groups. The elec...

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A New General Preparation of Polyfunctional Diarylamines by the Addition of Functionalized Arylmagnesium Compounds to Nitroarenes

Cited by 143 publications

References 20 publications

Smiles rearrangement for the synthesis of diarylamines

Smiles rearrangement for the synthesis of diarylamines

Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

Preparation and Reactions of Heteroaryl Organomagnesium Compounds

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