Magnetic Core-Shell Fe3O4@C-SO3H as an Efficient and Renewable ‘Green Catalyst’ for the Synthesis of O-2,3-Unsaturated Glycopyranosides

Guosheng Sun; Saifeng Qiu; Zekun Ding; Heshan Chen; Jiafen Zhou; Zhongfu Wang; Jianbo Zhang

doi:10.1055/s-0036-1588891

Synlett, Table of Contents

Synlett 2017; 28(03): 347-352
DOI: 10.1055/s-0036-1588891

letter

Magnetic Core-Shell Fe₃O₄@C-SO₃H as an Efficient and Renewable ‘Green Catalyst’ for the Synthesis of O-2,3-Unsaturated Glycopyranosides

Guosheng Sun

^aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn

,

Saifeng Qiu

^aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn

,

Zekun Ding

^aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn

,

Heshan Chen

^aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn

,

Jiafen Zhou

^aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn

,

Zhongfu Wang

^bSchool of Life Sciences, Northwest University, Xi’an, 710069, P. R. of China

,

Jianbo Zhang*

^aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn

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Abstract

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Abstract

A magnetic core-shell solid-acid catalyst Fe₃O₄@C-SO₃H was studied for synthesis of O-2,3-unsaturated glycosides through Ferrier rearrangement. The donors include 3,4,6-tri-O-acetyl-d-glucal and 3,4-di-O-acetyl-l-rhamnal. The acceptors consist of primary alcohols, secondary alcohols, tert-butanol, unsaturated alcohols, halogenated alcohol, sterol, sugars, and phenols. O-2,3-Unsaturated glycosides were obtained rapidly (<3 h) and efficiently (up to 98%) in good α selectivity (α/β >5:1 to 19:1). Moreover, the catalyst can be easily separated from the reaction with an external magnetic force and reused for a minimum of five times without any significant decrease in the yields of the products after every recycle, suggesting it a promising green catalyst in 2,3-unsaturated glycosides syntheses.

Key words

Fe₃O₄@C-SO₃H - magnetic core shell - recyclable catalyst - O-2,3-unsaturated glycosides - Ferrier rearrangement

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References

References and Notes

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16 Typical Experimental Procedure To a mixture of tri-O-acetyl-d-glucal (0.2 mmol, 54.4 mg), benzyl alcohol (26 μL, 0.24 mmol), and Fe₃O₄@C-SO₃H (30 mol%, 25 mg) in a round-bottom flask (10 mL), DCE (2 mL) was added, and the reaction mixture was stirred for 10 min at 80 °C. After completion of the reaction (monitored by TLC), the catalyst is separated from the reaction with an external magnetic force, and the catalyst was washed with CH₂Cl₂. The organic phase was combined and condensed under vacuum to get the crude product, which was purified by silica gel column chromatography PE–EtOAc = 6:1) to get 3a in 96% yield. All compounds were fully characterized by NMR spectroscopy and MS. Spectral and analytical data were in good agreement with the desired structures.
17 Selected Spectral Data Benzyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3a) Colorless oil. ¹H NMR (500 MHz, CDCl₃): δ = 7.40–7.33 (m, 5 H), 5.90 (d, J = 10.4 Hz, 1 H), 5.85 (dt, J = 10.2, 2.3 Hz, 1 H), 5.33 (dd, J = 9.4, 1.2 Hz, 1 H), 5.14 (s, 1 H), 4.81 (d, J = 11.7 Hz, 1 H), 4.69 (s, 1 H), 4.60 (d, J = 11.7 Hz, 1 H), 4.25 (dd, J = 11.6, 5.0 Hz, 1 H), 4.14–4.10 (m, 1 H), 2.08 (s, 3 H), 2.07 (s, 3 H) ppm. ESI-MS: m/z calcd for C₁₇H₂₀O₆Na [M + Na]⁺: 343.12; found: 343.15. Trichloroethyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyran-oside (3e) Colorless oil. ¹H NMR (500 MHz, CDCl₃): δ = 6.00 (d, J = 10.3 Hz, 1 H), 5.97–5.92 (m, 1 H), 5.36 (d, J = 9.2 Hz, 1 H), 5.30 (s, 1 H), 4.35 (d, J = 11.3 Hz, 1 H), 4.26–4.19 (m, 4 H), 2.11 (s, 3 H), 2.11 (s, 3 H) ppm. ESI-MS: m/z calcd for C₁₂H₁₅C_l3O₆Na [M + Na]⁺: 382.98; found: 382.94. tert-Butyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3h) Colorless oil. ¹H NMR (500 MHz, CDCl₃): δ = 5.85 (d, J = 10.1 Hz, 1 H), 5.78–5.71 (m, 1 H), 5.32 (s, 1 H), 5.30–5.24 (m, 1 H), 4.26–4.18 (m, 2 H), 4.17–4.12 (m, 1 H), 2.08 (s, 3 H), 2.08 (s, 3 H),1.29 (d, J = 2.6 Hz, 9 H) ppm. ESI-MS: m/z calcd for C₁₄H₂₂O₆Na [M + Na]⁺: 309.13; found: 309.17. Phenoxyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3m) Colorless oil. ¹H NMR (500 MHz, CDCl₃): δ = 7.05–7.34 (m, 5 H), 6.02–6.07 (m, 2 H), 5.73 (s, 1 H), 5.41–5.43 (dd, J = 9.5, 1.5 Hz, 1 H), 4.16–4.33 (m, 3 H), 2.14 (s, 3 H), 2.01 (s, 3 H) ppm. ESI-MS: m/z calcd for C₁₆H₁₈O₆Na [M + Na]⁺: 329.10; found: 329.17.

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