Synthesis of Anilines

Hartwig, John F.; Shekhar, Shashank; Shen, Qilong; Barrios‐Landeros, Fabiola

doi:10.1002/9780470682531.pat0391

Cited by 16 publications

(17 citation statements)

References 361 publications

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“…Most traditional methods for their synthesis from a corresponding C(sp 2 )-H bond involve multi-step sequences and/or, harsh conditions (6–8). In many instances, the initial product (nitro, azide, azo, nitroso, chloronitroso, amide/imide/sulfonamide, or imine) requires an additional step(s) before arriving at a free amine (6). The amination of organic anions is a useful and direct alternative (9), but is generally restricted to the introduction of –NR 1 R 2 (R 1 ,R 2 ≠ H) and is not applicable to base sensitive substrates.…”

Section: Main Textmentioning

confidence: 99%

Dirhodium-catalyzed C-H arene amination using hydroxylamines

Paudyal

Adebesin

Burt

et al. 2016

Science

247

139

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Primary and N-alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals and functional materials as well as in bioactive natural products. However, there is a dearth of generally applicable methods for the direct replacement of aryl hydrogens with –NH2/-NH-alkyl moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N-alkyl arylamines using either NH2/NHalkyl-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO2O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N-heterocycles.

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Section: Main Textmentioning

confidence: 99%

Dirhodium-catalyzed C-H arene amination using hydroxylamines

Paudyal

Adebesin

Burt

et al. 2016

Science

247

139

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“…Aromatic primary amines are key intermediates in fine chemicals, pharmaceuticals, agrochemicals, dyes, and material science . Similarly, their diazonium salts find several important applications in organic synthesis .…”

Section: Aminationmentioning

confidence: 99%

“…Similarly, their diazonium salts find several important applications in organic synthesis . The industrial production of aromatic amine relied on a two-stage process that involves the initial nitration of an arene and subsequent catalytic hydrogenation of the corresponding nitro compound . On the other hand, synthesis of amines utilizing aryl halides and ammonia is quite attractive, where selectivity and atom economy is desirable, particularly while dealing with functionalized amines. , Moreover, ammonia is one of the most abundant chemical feedstocks with more than 100 million tons produced annually through the Haber–Bosch process.…”

Section: Aminationmentioning

confidence: 99%

Copper-Mediated C–X Functionalization of Aryl Halides

Joseph¹,

Priyadarshini

2017

Org. Process Res. Dev.

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For more than a century, copper has been used as a promoter in cross-coupling reactions of aryl halides with diverse nucleophiles to construct C−C and C-heteroatom bonds. The discovery of rate acceleration effect of organic ligands has expanded the scope of copper catalysis, facilitating to conduct new reactions under ambient conditions, allowing the selective C−X functionalization of aryl halides with diverse sensitive functionalities in a single step. This review confers the advancements in copper-mediated direct transformation of aryl halides in to trifluoromethylated arenes, aryl nitriles, phenols, aryl thiols, anilines, and nitroarenes and also the mechanistic aspects of these reactions.

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“…Because of these important applications, numerous classical and modern methods for the preparation of anilines have been reported. 7 …”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Arylation of Fluoroalkylamines

2015

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We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond.

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Synthesis of Anilines

Abstract: Introduction Uncatalyzed Reactions Palladium‐Catalyzed Methods Mechanism of Palladium‐Catalyzed Amination of Aryl Halides Copper‐Mediated Methods Mechanism of Copper‐Mediated/Catalyzed Reactions

Cited by 16 publications

References 361 publications

Dirhodium-catalyzed C-H arene amination using hydroxylamines

Dirhodium-catalyzed C-H arene amination using hydroxylamines

Copper-Mediated C–X Functionalization of Aryl Halides

Palladium-Catalyzed Arylation of Fluoroalkylamines

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