Direct Reductive <i>N</i>‐Functionalization of Aliphatic Nitro Compounds

Rauser, Marian; Ascheberg, Christoph; Niggemann, Meike

doi:10.1002/chem.201705986

Cited by 23 publications

(8 citation statements)

References 62 publications

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“…Finally, amination with the more challenging nitroalkanes was evaluated, in which only Niggemann's very recent approach was able to succeed . Preliminary results under conventional heating at 100 °C showcased low conversion and so, MW irradiation was tested.…”

Section: Methodsmentioning

confidence: 99%

Reductive Molybdenum‐Catalyzed Direct Amination of Boronic Acids with Nitro Compounds

et al. 2019

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The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C−N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. Moreover, this general and step‐economical synthesis of aromatic secondary amines showcases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.

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Section: Methodsmentioning

confidence: 99%

Reductive Molybdenum‐Catalyzed Direct Amination of Boronic Acids with Nitro Compounds

et al. 2019

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“…Conversely, although methods for the synthesis of aminoboranes have significantly advanced, their application lags disturbingly behind . Recently, we realized a highly efficient method for the preparation of aliphatic aminoboranes from nitro compounds, enabled by a combination of B 2 pin 2 and zinc organyls . Since the reaction showed a high generality for the preparation of functionalized aminoboranes, we became interested in their processing.…”

Section: Methodsmentioning

confidence: 99%

“…[13] Conversely,a lthough methods for the synthesis of aminoboranes have significantly advanced, [14] their application lags disturbingly behind. [16] Since the reaction showed ah igh generality for the preparation of functionalized aminoboranes,w eb ecame interested in their processing. [16] Since the reaction showed ah igh generality for the preparation of functionalized aminoboranes,w eb ecame interested in their processing.…”

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confidence: 99%

O₂‐Mediated Oxidation of Aminoboranes through 1,2‐N Migration

2018

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In analogy to the classical reaction of C-B bonds with peroxides, the first oxidative functionalization of aminoboranes through a 1,2-N migration was realized. Readily available aliphatic nitro compounds are thereby transformed into N- and O-functionalized hydroxylamines in a single synthetic operation. Addition of hazardous peroxides is avoided. Instead, the insertion of O , as the terminal oxidant, into Zn-C bonds provides the necessary peroxides. The required zinc organyls, in turn, are formed through a boron-to-zinc exchange, from an organoboronic ester byproduct of the nitro-to-aminoborane transformation.

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“…Thus, clearly, practical step and redox efficient strategies to build the indole scaffold are still in high demand, in particular using non-ortho functionalized nitroarenes. Herein, we propose to develop such a strategy, by directly intercepting the reduction of the nitroarene substrate [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] to achieve a straightforward Rh-catalysed C-H bond activation [47][48][49][50][51][52] event and coupling with the alkyne. We thus started with nitrobenzene and diphenylacetylene as model substrates, in the presence of catalytic amounts of the classical [Cp*RhCl 2 ] 2 dimer.…”

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confidence: 99%