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Synlett 2014; 25(6): 835-842
DOI: 10.1055/s-0033-1340844
DOI: 10.1055/s-0033-1340844
letter
Magnetic Nano Fe3O4 Catalyzed Solvent-Free Stereo- and Regioselective Aminolysis of Epoxides by Amines; a Green Method for the Synthesis of β-Amino Alcohols
Authors
Weitere Informationen
Publikationsverlauf
Received: 11. Dezember 2013
Accepted after revision: 28. Januar 2014
Publikationsdatum:
06. März 2014 (online)
Abstract
We report the use of magnetic nano Fe3O4 as a mild heterogeneous catalyst for the aminolysis of epoxides with amines. The approach constitutes a green method for the formation of a variety of β-amino alcohols with very high stereo- and regioselectivity under solvent-free and ambient reaction conditions. The aminolysis of chiral epoxides with amines gave the corresponding chiral β-amino alcohols with complete inversion of stereochemistry. The magnetic nano Fe3O4 catalyst can be easily recovered and recycled.
Key words
amino alcohols - epoxides - green chemistry - nano magnetite - regioselectivity - stereoselective synthesisSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information (PDF)
-
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- 9a Generally, the reactions were carried out by using 1 (1.5 mmol), amine 2 (1 mmol) and nano Fe3O4 (10 mol%) without solvent and open to the atmosphere for 20 h. See the respective tables for individual entries.
- 9b General Experimental Procedure: Epoxide (1.5–2 mmol), amine (1.0 mmol) and nano Fe3O4 (10 mol%, 23 mg, particle size = <50 nm) were stirred at r.t. open to the atmosphere for 20 h. EtOAc (1–2 mL) was then added and the mixture was stirred for 1–2 min. A magnet was then externally applied to the flask and the catalyst was allowed to accumulate at the walls of the flask; the resulting clear solution was transferred to a fresh flask by using a pipette. This step was repeated twice more, and the combined organic layers were dried over anhydrous Na2SO4, filtered, and the solvent evaporated. Purification by column chromatography on silica gel (EtOAc–hexanes, 20:80) gave the pure products.
- 9c All the reactions were carried out at r.t (range 28–32 °C) unless otherwise mentioned.
- 9d When one of the substrates (epoxide or amine) was a solid, to facilitate homogeneous stirring, the reaction was carried out by using 1 mmol of the solid sample and the other corresponding liquid sample in excess (2 mmol) and the yield was calculated based on the limiting reagent.
- 10 All the reactions were regioselective and gave only a single regioisomer. We were not able to isolate any of the corresponding minor regioisomers for characterization. The identity of all compounds obtained in this work was established by comparison of their spectroscopic data with reported data and we also confirmed the structure of representative regioisomers from the X-ray structures of 5c, 5e, 5h, and 5k. Their crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (5c; CCDC-976219, 5e; CCDC-976220, 5h; CCDC-976221 and 5k; CCDC-976222). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.