Magnetic Nano Fe3O4 Catalyzed Solvent-Free Stereo- and Regioselective ­Aminolysis of Epoxides by Amines; a Green Method for the Synthesis of β-Amino Alcohols

Amit Kumar; Ramarao Parella; Srinivasarao Arulananda Babu

doi:10.1055/s-0033-1340844

Synlett, Table of Contents

Synlett 2014; 25(6): 835-842
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

Amit Kumar

Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali, Manauli P.O., Sector 81, SAS Nagar, Mohali, Knowledge City, Punjab 140306, India Fax: +91(172)2240266 Email: sababu@iisermohali.ac.in
Ramarao Parella

Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali, Manauli P.O., Sector 81, SAS Nagar, Mohali, Knowledge City, Punjab 140306, India Fax: +91(172)2240266 Email: sababu@iisermohali.ac.in
Srinivasarao Arulananda Babu*

Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali, Manauli P.O., Sector 81, SAS Nagar, Mohali, Knowledge City, Punjab 140306, India Fax: +91(172)2240266 Email: sababu@iisermohali.ac.in

Abstract

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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 synthesis

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References

References and Notes

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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.

Supplementary Material

Supporting Information (PDF)

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

Magnetic Nano Fe₃O₄ Catalyzed Solvent-Free Stereo- and Regioselective Aminolysis of Epoxides by Amines; a Green Method for the Synthesis of β-Amino Alcohols