Recyclable cooperative catalyst for accelerated hydroaminomethylation of hindered amines in a continuous segmented flow reactor

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 increas...

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Bibliographic Details
Published in:Nature communications 2022-05, Vol.13 (1), p.2441-2441, Article 2441
Main Authors: Ibrahim, Malek Y. S., Abolhasani, Milad
Format: Article
Language:English
Subjects:
140/131
639/166/898
639/638/77/888
Amines
Batch reactors
Catalysts
Chemical activity
Chemical reactions
Condensates
Cooperation
Equilibrium
Humanities and Social Sciences
Hydrogen bonds
Hydrogenation
Ligands
Manufacturing
multidisciplinary
Optimization
Organic light emitting diodes
Reactors
Recycling
Rhodium
Science
Science (multidisciplinary)
Selectivity
Solvents
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Summary: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. Online reaction optimization expands the scope to include alkyl, aryl, and primary amines. In-flow solvent tuning enables selectivity switching from amine to enamine without the need for changing the ligand. Furthermore, leveraging the ionic nature of the catalyst, we present a robust Rh recovery strategy up to 4 recycles without loss of activity. Flow chemistry enables intensified production of hindered amines. Here the authors present a rapid and reusable catalyst to operate in a segmented flow reactor for olefin hydroaminomethylation to selectively produce hindered amines or enamines.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-022-30175-0