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Synthesis 2019; 51(07): 1585-1594
DOI: 10.1055/s-0037-1610681
DOI: 10.1055/s-0037-1610681
paper
One-Pot Synthesis of N-Arylated Amines by Hydroaminomethylation of 2,5-Dihydrofuran with Aromatic Amines
This work was supported by the National Natural Science Foundation of China (21633013, 21073211, 21174155) and Key Research Program of Science and Technology Project of Gansu province (18YF1GA124).Further Information
Publication History
Received: 26 September 2018
Accepted after revision: 21 November 2018
Publication Date:
16 January 2019 (online)
Abstract
A new efficient catalytic system for one-step synthesis of N-arylated amines, for example, an important intermediate, 4-ethyl-N-[(tetrahydrofuran-3-yl)methyl]aniline, is achieved by using different rhodium precursor and phosphorus ligands catalyzed hydroaminomethylation of aniline and its derivatives with heterocyclic and/or cyclic olefins. By screening the reaction parameters, the optimal reaction conditions are found as follows: methanol as a solvent, PPh3 as a ligand, [Rh(cod)2]BF4 as a catalyst precursor, a P/Rh ratio of 5:1, syngas pressure 4 MPa (H2/CO = 3:1), 100 °C, 20 hours, and no additives. The conversion of aniline reaches >99% and the yield of N-[(tetrahydrofuran-3-yl)methyl]aniline is up to 99% using this catalytic system. Moreover, the reaction of aniline and various cyclic olefins is investigated under the optimal conditions, and excellent conversion and good yields are obtained.
Key words
heterocyclic olefins - cyclic olefins - hydroaminomethylation - amines - phosphine/Rh - 2,5-dihydrofuranSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610681.
- Supporting Information
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