A highly chemo- and regioselective hydroaminomethylation of simple as well as functionalized alpha-olefins using a cationic rhodium precatalyst together with Xantphos as ligand is reported. Studies of the influence of ligands and reaction conditions led to an unprecedented selective hydroaminomethylation procedure. The novel procedure constitutes an economically attractive and environmentally favorable synthesis of secondary and tertiary aliphatic amines.
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A biphosphine copolymer encapsulated single-site Rh catalyst for heterogeneous regioselective hydroaminomethylation of alkenes.
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July 2022
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, No. 18, Tianshui Middle Road, Lanzhou, 730000, P. R. China.
A novel porous organic polymer catalyst with encapsulated single-site Rh (Rh@CPOL-DPMphos&-3vPPh) was developed and employed in heterogeneous hydroaminomethylation of alkenes, affording the corresponding amines in good to excellent regioselectivity and catalytic activity by a one-pot method. The combined actions of hierarchical pore confinement and the biphosphine ligand derived from the POP catalyst contributed to the improved regioselectivity.
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Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, NC, 27695, USA.
Synthesis of hindered amines using the atom-efficient hydroaminomethylation (HAM) route remains a challenge. Here, we report a general and accelerated HAM in segmented flow, achieved via a cooperative effect between rhodium (Rh)/N-Xantphos and a co-catalyst (2-Fluoro-4-methylbenzoic acid) to increase the reactivity by 70 fold when compared to Rh/Xantphos in batch reactors. The cooperation between Rh and the co-catalyst facilitates the cleavage of the H-H bond and drives the equilibrium-limited condensation step forward.
View Article and Find Full Text PDFA Selective and General Cobalt-Catalyzed Hydroaminomethylation of Olefins to Amines.
Angew Chem Int Ed Engl
January 2022
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
A new cobalt catalyst is presented for the domino hydroformylation-reductive amination reaction of olefins. The optimal Co-tert-BuPy-Xantphos catalyst shows good to excellent linear-to-branched (n/iso) regioselectivity for the reactions of aliphatic alkenes with aromatic amines under mild conditions. This system is far more selective than traditional cobalt(I) catalysts and even better than most known rhodium catalysts.
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Laboratoire Hétérochimie Fondamentale et Appliquée, Université Toulouse 3-Paul Sabatier, CNRS UMR 5069, 118 Route de Narbonne, 31062, Toulouse Cedex 9, France.
Article Synopsis
- The study presents a Rh-catalyzed hydroaminomethylation reaction that efficiently converts terminal alkenes into linear amines using glycerol under mild conditions.
- This method achieves moderate to excellent yields with low catalyst loading and pressure while avoiding unwanted side reactions.
- The research highlights glycerol's role in hydrogen transfer and demonstrates Rh's unique ability to prevent aldol condensation, maintaining the reaction's selectivity and efficiency.
Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes.
Chem Rev
April 2018
Laboratoire de Chimie de Coordination du CNRS UPR 8241 , Composante ENSIACET de l'Institut National Polytechnique de Toulouse, University of Toulouse UPS-INP, 4 allée Emile Monso , 31030 Toulouse Cedex 4 , France.
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