Efficient Rhodium‐Catalyzed Multicomponent Reaction for the Synthesis of Novel Propargylamines |
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| Authors: | Dr. Laura Rubio‐Pérez Dr. Manuel Iglesias Julen Munárriz Dr. Victor Polo Prof. Dr. Jesús J. Pérez‐Torrente Prof. Dr. Luis A. Oro |
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| Affiliation: | 1. Departamento Química Inorgánica ‐ ISQCH, Universidad de Zaragoza ‐ CSIC, Pedro Cerbuna 12, 50009 Zaragoza (Spain);2. Departamento Química Física, Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain);3. King Fahd University of Petroleum & Minerals (KFUPM), Dhahran 31261 (Saudi Arabia) |
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| Abstract: | [{Rh(μ‐Cl)(H)2(IPr)}2] (IPr = 1,3‐bis‐(2,6‐diisopropylphenyl)imidazole‐2‐ylidene) was found to be an efficient catalyst for the synthesis of novel propargylamines by a one‐pot three‐component reaction between primary arylamines, aliphatic aldehydes, and triisopropylsilylacetylene. This methodology offers an efficient synthetic pathway for the preparation of secondary propargylamines derived from aliphatic aldehydes. The reactivity of [{Rh(μ‐Cl)(H)2(IPr)}2] with amines and aldehydes was studied, leading to the identification of complexes [RhCl(CO)IPr(MesNH2)] (MesNH2 = 2,4,6‐trimethylaniline) and [RhCl(CO)2IPr]. The latter shows a very low catalytic activity while the former brought about reaction rates similar to those obtained with [{Rh(μ‐Cl)(H)2(IPr)}2]. Besides, complex [RhCl(CO)IPr(MesNH2)] reacts with an excess of amine and aldehyde to give [RhCl(CO)IPr{MesN?CHCH2CH(CH3)2}], which was postulated as the active species. A mechanism that clarifies the scarcely studied catalytic cycle of A3‐coupling reactions is proposed based on reactivity studies and DFT calculations. |
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| Keywords: | C H activation hydroalkynylation multicomponent reactions propargylamines rhodium |
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