Copper(II) Triflate Catalyzed Rearrangement of Amino 2,3-Epoxides to α-Amino Ketones

Saranya Chitsomkhuan; Supawadee Buakaew; Joseph S. M. Samec; Pitak Chuawong; Jenjira Saymaya; Punlop Kuntiyong; Wanchai Pluempanupat; Sunisa Akkarasamiyo

doi:10.1055/s-0043-1775367

Synlett, Table of Contents

Synlett 2025; 36(02): 157-160
DOI: 10.1055/s-0043-1775367

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Copper(II) Triflate Catalyzed Rearrangement of Amino 2,3-Epoxides to α-Amino Ketones

Saranya Chitsomkhuan

^aDepartment of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand

,

Supawadee Buakaew

^aDepartment of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand

,

Joseph S. M. Samec

^bDepartment of Organic Chemistry, Stockholm University, 106 91, Stockholm, Sweden

,

Pitak Chuawong

^cDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Special Research Unit for Advanced Magnetic Resonance (AMR), Kasetsart University, Bangkok 10900, Thailand

,

Jenjira Saymaya

^aDepartment of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand

,

Punlop Kuntiyong

^dDepartment of Chemistry, Faculty of Science, Silpakorn University, Nakhon Pathom, 73000, Thailand

,

Wanchai Pluempanupat

^cDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Special Research Unit for Advanced Magnetic Resonance (AMR), Kasetsart University, Bangkok 10900, Thailand

,

Sunisa Akkarasamiyo∗

^aDepartment of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand

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Abstract

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Abstract

α-Amino ketones were synthesized by a Meinwald rearrangement of biomass-based amino epoxides using copper(II) triflate as a catalyst. The regioselectivity of the rearrangement can be rationalized in terms of the reaction proceeding via the most stable carbocationic intermediate to give various α-amino α′-aryl ketones in moderate to good yields. This is an attractive method to prepare α-amino ketones using a benign and inexpensive catalyst.

Key words

Meinwald rearrangement - amino ketones - amino epoxide - copper catalysis - copper triflate

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References

References and Notes

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18 Rearrangement of α-Amino Epoxides 1; General Procedure A dried tube was charged with Cu(OTf)₂ (1 mol%) then capped and flushed with argon. A solution of the appropriate α-amino epoxide 1 (1 mmol) in anh 1,4-dioxane (4 mL) was added, and the mixture was stirred at 80 °C for 2 h. Sat. aq NaHCO₃ was added, and the mixture was extracted with EtOAc. The combined organic layers were dried (Na₂SO₄) and the solvent was evaporated under reduced pressure, then the mixture was then purified by column chromatography (silica gel, EtOAc–hexane gradient). N-Cyclohexyl-2-nitro-N-(2-oxo-3-phenylpropyl)benzenesulfonamide (2a) Yellow oil; yield: 250 mg (60%). ¹H NMR (400 MHz, CDCl₃): δ = 8.16–8.11 (m, 1 H), 7.72–7.60 (m, 3 H), 7.39–7.23 (m, 5 H), 4.21 (s, 2 H), 3.80 (s, 2 H), 3.71 (tt, J = 12.1, 3.5 Hz, 1 H), 1.74–1.52 (m, 5 H), 1.31–1.20 (m, 2 H), 1.09–0.81 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 203.3, 148.0, 134.1, 133.5, 133.3, 131.7, 131.2, 129.5 (2C), 128.9 (2C), 127.3, 124.1, 58.2, 51.2, 46.7, 31.2 (2 C), 25.7 (2 C), 25.1. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₁H₂₄N₂NaO₅S: 439.1298; found: 439.1368.

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