Palladium doping of In<sub>2</sub>O<sub>3</sub> towards a general and selective catalytic hydrogenation of amides to amines and alcohols

Sorribes, Iván; Lemos, Samantha C.S.; Martı́n, Santiago; Mayoral, Álvaro; Lima, Ronaldo Cintra; Andrés, Juán

doi:10.1039/c9cy02128k

Cited by 22 publications

(21 citation statements)

References 190 publications

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“…In contrast, the direct hydrogenation (30 bar H2) of N-methylformanilide 2c provided a mixture of N-methylaniline 2a and N,N-dimethylaniline 2b with a 50 to 60 % yield depending on the conditions. This is consistent with recent results published by Sorribes et al, 21 whereas only traces of the de-methylated product were observed with FA (Table 3, entries 2, 3). A higher H2 pressure (50 bar) did not significantly modify the results, and a CO2 pressure only had a marginal impact (Table 3, Entries 3, 4).…”

supporting

confidence: 93%

Additive-free selective methylation of secondary amines with formic acid over a Pd/In₂O₃ catalyst

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Benaissa

Godou

et al. 2022

Catal. Sci. Technol.

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confidence: 93%

Additive-free selective methylation of secondary amines with formic acid over a Pd/In₂O₃ catalyst

Genre

Benaissa

Godou

et al. 2022

Catal. Sci. Technol.

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“…In contrast, the direct hydrogenation (30 bar H2) of N-methylformanilide 2c provided a mixture of Nmethylaniline 2a and N,N-dimethylaniline 2b with a 50 to 60 % yield depending on the conditions. This is consistent with recent results published by Sorribes et al, 18 whereas only traces of the de-methylated product were observed with FA (Table 3, entries 2, 3). A higher H2 pressure (50 bar) did not significantly modify the results, and a CO2 pressure only had a marginal impact (Table 3, Entries 3, 4).…”

supporting

confidence: 93%

Additive-free selective methylation of amines with formic acid over a Pd/In2O3 catalyst

Genre

Benaissa

Godou

et al. 2021

Preprint

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“…Both catalysts showed reusability and selectivity towards the hydrogenation of arenes. Finally, very recently Sorribes, Andrés and co-workers reported a reusable [Pd/In 2 O 3 ] material able to perform the hydrogenation of amides through a C–N cleavage pathway with an improved substrate scope and selectivity in comparison with previous examples (Table 1 , entry 16) 83 . Interestingly, the active material is constituted by Pd 2+ cationic species monoatomically dispersed in the oxide matrix.…”

Section: Development Of Heterogeneous Catalystsmentioning

confidence: 99%

“…In 2018, the groups of Milstein and Tomishige reported the first heterogeneous catalysts able to perform efficiently the hydrogenation of amides through C-N cleavage. 83 . Interestingly, the active material is constituted by Pd 2+ cationic species monoatomically dispersed in the oxide matrix.…”

Section: Development Of Heterogeneous Catalystsmentioning

confidence: 99%

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

et al. 2020

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Catalytic hydrogenation of amides is of great interest for chemists working in organic synthesis, as the resulting amines are widely featured in natural products, drugs, agrochemicals, dyes, etc. Compared to traditional reduction of amides using (over)stoichiometric reductants, the direct hydrogenation of amides using molecular hydrogen represents a greener approach. Furthermore, amide hydrogenation is a highly versatile transformation, since not only higher amines (obtained by CO cleavage), but also lower amines and alcohols, or amino alcohols (obtained by C-N cleavage) can be selectively accessed by fine tuning of reaction conditions. This review describes the most recent advances in the area of amide hydrogenation using H 2 exclusively and molecularly defined homogeneous as well as nanostructured heterogeneous catalysts, with a special focus on catalyst development and synthetic applications. T he development of green and sustainable methods is a central focus of modern organic synthesis and its applications in various areas of the chemical industry. In this respect, many reduction reactions, traditionally employing stoichiometric amounts of metal hydrides with inherent low atom efficiency 1 , can be favorably replaced by catalytic hydrogenations. In fact, the combination of molecular hydrogen and catalysts does not only allow avoiding formation of waste products 2 , it also opens the door to clean transformations based on renewable energies as the conversion of solar or wind energy to "green" hydrogen is likely to be implemented in the coming years. Among the many reduction reactions known, amide hydrogenation can be encountered as one of the most desired considering the importance of the derived amines in several branches of chemical industry. In fact, since the start of the Green Chemistry Institute Pharmaceutical Roundtable in the United States in 2005, several projects aimed to the achievement of a practical amide hydrogenation methodology have been supported 3,4. The long-term interest of the pharmaceutical industry in this specific transformation is explained by the fact that it ideally affords structurally complex amines, present in many of the currently employed drugs. Furthermore, amines are also in bulk and fine chemicals used in the manufacture of plastics, textiles, surfactants, dyes, and many more 5. Amides play a central role in the chemistry of life, as they are the key elements to generate peptides and proteins from amino acid monomers. At the same time, they are present in artificial

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Palladium doping of In₂O₃ towards a general and selective catalytic hydrogenation of amides to amines and alcohols

Abstract: The first general heterogeneous hydrogenation of amides to amines and alcohols is performed under additive-free conditions and without product de-aromatization by applying a Pd-doped In2O3 catalyst.

Cited by 22 publications

References 190 publications

Additive-free selective methylation of secondary amines with formic acid over a Pd/In₂O₃ catalyst

Additive-free selective methylation of secondary amines with formic acid over a Pd/In₂O₃ catalyst

Additive-free selective methylation of amines with formic acid over a Pd/In2O3 catalyst

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

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Palladium doping of In2O3 towards a general and selective catalytic hydrogenation of amides to amines and alcohols

Abstract: The first general heterogeneous hydrogenation of amides to amines and alcohols is performed under additive-free conditions and without product de-aromatization by applying a Pd-doped In2O3 catalyst.

Cited by 22 publications

References 190 publications

Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst

Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst

Additive-free selective methylation of amines with formic acid over a Pd/In2O3 catalyst

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

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Palladium doping of In₂O₃ towards a general and selective catalytic hydrogenation of amides to amines and alcohols

Additive-free selective methylation of secondary amines with formic acid over a Pd/In₂O₃ catalyst

Additive-free selective methylation of secondary amines with formic acid over a Pd/In₂O₃ catalyst