Synlett 2017; 28(03): 347-352
DOI: 10.1055/s-0036-1588891
letter
© Georg Thieme Verlag Stuttgart · New York

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

Guosheng Sun
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China   Email: Jbzhang@chem.ecnu.edu.cn
,
Saifeng Qiu
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China   Email: Jbzhang@chem.ecnu.edu.cn
,
Zekun Ding
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China   Email: Jbzhang@chem.ecnu.edu.cn
,
Heshan Chen
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China   Email: Jbzhang@chem.ecnu.edu.cn
,
Jiafen Zhou
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China   Email: Jbzhang@chem.ecnu.edu.cn
,
Zhongfu Wang
b   School of Life Sciences, Northwest University, Xi’an, 710069, P. R. of China
,
Jianbo Zhang*
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China   Email: Jbzhang@chem.ecnu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 23 July 2016

Accepted after revision: 06 September 2016

Publication Date:
06 October 2016 (online)


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.

Supporting Information

 
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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 C12H15Cl3O6Na [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.