New Iridium Catalysts for the Efficient Alkylation of Anilines by Alcohols under Mild Conditions

Michlik, Stefan; Kempe, Rhett

doi:10.1002/chem.201001871

Cited by 156 publications

(38 citation statements)

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“…To our delight, N-alkylated products were afforded in 83 and 95% yield (Entries 14-15). 3-Isopropylaniline and 4-tert-butylaniline could also react smoothly to generate the corresponding amines in good yields (Entries [16][17]. In addition, our catalytic system was also suitable for alkylation of aliphatic amines.…”

Section: Resultsmentioning

confidence: 95%

“…Initially, the N-alkylation of amines with alcohols was carried out in the presence of various kinds of homogeneous transition-metal catalysts including ruthenium [9][10][11] , platinum 12 , iridium [13][14][15][16][17][18] , silver 19 and palladium 20 ，Cu/Nibased 29 , Ni-Cu/Al 2 O 3 30 and Fe 3 O 4 31 , were developed for the Nalkylation of amines. However, it is still extremely challenging to require harsh reaction conditions such as high temperature and strong base or using noble metal.…”

Section: Introductionmentioning

confidence: 99%

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Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO₂

Zhang

Deng

et al. 2015

Catal. Sci. Technol.

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It is highly desirable to develop efficient heterogeneous photocatalysts for organic reactions. Here, we show the preparation and catalytic performance of a novel TiO 2 (P25) supported Cu and Mo photocatalyst (Cu-Mo/TiO 2 ) for N-alkylation of amines with alcohols under UV irradiation at room temperature. A variety of aromatic and aliphatic amines were selectively converted into the corresponding secondary amines or tertiary amines in moderate to excellent yields without the addition of any co-catalysts such as bases and organic ligands. Noteworthy, this catalytic system is feasible in the alkylation of anilines containing halogen substituents with alcohols and the yields of the desired products are up to 95%.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO₂

Zhang

Deng

et al. 2015

Catal. Sci. Technol.

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“…However, heterobidentate P,N-donor ligands have emerged lately as an important class of ligands that have been applied in various catalytic transformations, such as hydrogenation of alkenes [1,2], hydrogen transfer reactions [3], Suzuki-Miyura couplings [4,5], arylation of unactivated arenes [6], alkylation of anilines by alcohols [7] and allylic substitution [8,9], among others. Nevertheless, this type of ligands has been scarcely used in metal catalyzed carbonylation reactions, and almost in all reported cases Pd was the metal used.…”

Section: Introductionmentioning

confidence: 99%

Methoxycarbonylation of Styrene Using a New Type of Palladium Complexes Bearing P,N-donor Ligands as Catalysts

et al. 2015

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Artículo de publicación ISIPalladium complexes of the type [Pd(L)Cl(PPh3)]Cl (L = 2-diphenylphosphinoamino)pyrimidine, or 2-diphenylphosphinoaniline), generated in situ by addition of one equivalent of PPh3 to the corresponding neutral complexes [Pd(L)Cl-2], were tested as catalysts for the methoxycarbonylation of styrene. The catalyst containing the pyrimidinyl ligand shows almost complete chemo- and regioselectivity together with a high conversion rate. However, in identical conditions, the [Pd(Ph2PNHC6H4PPh2)Cl-2] complex, where the P,N-ligand has been replaced by a related bidentate P-donor one, shows a significantly lesser performance.Fondecyt-Chile 112014

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“…In this context, of particular importance is the N-alkylation of amines with alcohols to synthesize structurally complex primary and/or secondary amine compounds, which represents one of the most straightforward, efficient and eco-friendly methodologies for amine synthesis. As a consequence, a number of homogeneous and heterogeneous metal catalysts (e.g., Pt [20,21], Pd [22], Ru [23][24][25][26][27][28][29], Ir [30][31][32][33][34], Au [35], Fe [36][37][38][39], Mn [40,41], and Co [42][43][44][45]) have been developed for such a reaction (Scheme 1a). Despite great and alcohols with high activity and selectivity via the borrowing hydrogen strategy remains challenging.…”

Section: Introductionmentioning

confidence: 99%

Switchable Access to Amines and Imines from Reductive Coupling of Nitroarenes with Alcohols Catalyzed by Biomass-Derived Cobalt Nanoparticles

et al. 2019

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Cobalt nanoparticles modified with N-doped hierarchical porous carbon derived from biomass are found to be a highly efficient, reusable heterogeneous catalyst for the coupling of nitroarenes with alcohols, selectively affording imines and amines via the borrowing hydrogen strategy for the first time. The product selectivity between imine and amine may be precisely tuned by simple alteration of the reaction conditions without changing the catalyst in one reaction system. In this study, a broad set of complex imines and amines was successfully synthesized in good to high yields with various functional groups tolerated for both nitroarenes and alcohols, highlighting the potentially practical utility of the protocol. This heterogeneous catalyst can be easily removed from the reaction medium by external magnet and can be reused at least four times without significant loss in activity and selectivity.Catalysts 2019, 9, 116 2 of 11 achievements, direct synthesis of imines by the coupling of nitroarenes and alcohols with high activity and selectivity via the borrowing hydrogen strategy remains challenging. To date, only a handful of examples enabled by noble metal catalysts (e.g., Pd [46,47], Ru [48], Ir [49], and Au [50,51]) have been reported; however, their catalytic activities and selectivities are rather low and accompanied by limited substrate scopes (Scheme 1b). In addition, the high cost and limited reserve on earth of noble metal catalysts significantly impedes their large-scale industrial application. Notably, no successful direct imine formation from nitroarenes and alcohols catalyzed by heterogeneous base metal catalysts has been described, to the best of our knowledge.

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New Iridium Catalysts for the Efficient Alkylation of Anilines by Alcohols under Mild Conditions

Cited by 156 publications

References 50 publications

Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO₂

Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO₂

Methoxycarbonylation of Styrene Using a New Type of Palladium Complexes Bearing P,N-donor Ligands as Catalysts

Switchable Access to Amines and Imines from Reductive Coupling of Nitroarenes with Alcohols Catalyzed by Biomass-Derived Cobalt Nanoparticles

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New Iridium Catalysts for the Efficient Alkylation of Anilines by Alcohols under Mild Conditions

Cited by 156 publications

References 50 publications

Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO2

Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO2

Methoxycarbonylation of Styrene Using a New Type of Palladium Complexes Bearing P,N-donor Ligands as Catalysts

Switchable Access to Amines and Imines from Reductive Coupling of Nitroarenes with Alcohols Catalyzed by Biomass-Derived Cobalt Nanoparticles

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Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO₂

Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO₂