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Synlett 2023; 34(03): 288-292
DOI: 10.1055/a-1969-3992
DOI: 10.1055/a-1969-3992
letter
Total Synthesis of Phellinus ribis Glycans with Immunostimulating Activities by an Orthogonal One-Pot Glycosylation Strategy
The research was supported by National Natural Science Foundation of China (22271294), the Key Project of the Natural Science Foundation of Yunnan Province (No. 202101AS070030), the CAS Pioneer Hundred Talents Program (No. 2017-128), the Young Talents Project of High-level Talent Introduction Program of Yunnan Province.
Abstract
A total synthesis of nonasaccharide repeating units and shorter sequences from Phellinus ribis glycans with strong immunostimulating activities was achieved by an orthogonal one-pot glycosylation strategy based on an N-phenyltrifluoroacetimidate glycosylation, a Yu glycosylation, and an ortho-(1-phenylvinyl)benzoate glycosylation. The issues inherent to thioglycosides-based orthogonal one-pot glycosylations, such as aglycone transfer, are eliminated by this one-pot glycosylation strategy, which streamlines the chemical synthesis of glycans.
Key words
Phellinus ribis - glycans - one-pot reaction - glycosylation - total synthesis - oligosaccharidesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1969-3992.
- Supporting Information
Publication History
Received: 17 August 2022
Accepted after revision: 27 October 2022
Accepted Manuscript online:
27 October 2022
Article published online:
23 November 2022
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- 26 Tetrasaccharide 3; Typical ProcedureA solution of 10 (162.0 mg, 0.077 mmol) in 1:1 MeOH–CH2Cl2 (2 mL) was adjusted to pH 12 by the addition of NaOMe, and the mixture was stirred overnight at rt. The mixture was then neutralized to pH 7 with 1 M aq HCl, filtered, and concentrated. The residue was purified by column chromatography [Sephadex LH 20, MeOH–CH2Cl2 (1:1)] to give an intermediate; yield: 116.0 mg (89%).A mixture of the intermediate (50.0 mg, 0.029 mmol) and 10% Pd/C (316.8 mg) in EtOAc (3 mL)–MeOH (7 mL)–H2O (0.7 mL)–HOAc (0.07 mL) was stirred under H2 at rt for 2 d, then filtered and concentrated in vacuo. The residue was purified over a Sephadex TM LH-20 column (H2O) to give 3 as a white solid; yield: 18.6 mg (81%); [α]D 25 –18.93 (c 0.120, H2O).1H NMR (400 MHz, D2O): δ = 4.72 (d, J = 8.0 Hz, 1 H), 4.51 (dd, J = 8.0, 6.4 Hz, 2 H), 4.45 (d, J = 8.0 Hz, 1 H), 4.23–4.16 (m, 2 H), 3.94–3.80 (m, 5 H), 3.76–3.57 (m, 6 H), 3.53–3.22 (m, 13 H), 3.00 (t, J = 7.5 Hz, 2 H), 1.71–1.62 (m, 4 H), 1.47–1.39 (m, 2 H). 13C NMR (151 MHz, D2O): δ = 102.88, 102.78, 102.57, 102.16, 84.31, 75.96, 75.66, 75.52, 75.47, 74.85, 74.81, 73.40, 73.01, 72.96, 72.80, 70.14, 69.51, 69.38, 69.26, 68.73, 68.54, 68.07, 60.63, 60.59, 39.32, 28.14, 26.43, 25.08, 22.05. HRMS (ESI): m/z [M + H]+ calcd for C29H54NO21: 752.3183; found: 752.3191.Hexasaccharide 2Prepared from 7, and purified over a Sephadex LH-20 column (H2O) as a white solid; yield: 35 mg (86%); [α]D 25 –28.68 (c 0.08, H2O). 1H NMR (400 MHz, D2O): δ = 4.73 (d, J = 8.0 Hz, 1 H), 4.55–4.48 (m, 4 H), 4.45 (d, J = 8.0 Hz, 1 H), 4.24–4.16 (m, 4 H), 3.94–3.81 (m, 7 H), 3.77–3.56 (m, 9 H), 3.53–3.43 (m, 9 H), 3.43–3.21 (m, 9 H), 2.99 (t, J = 7.5 Hz, 2 H), 1.72–1.60 (m, 4 H), 1.49–1.40 (m, 2 H). 13C NMR (201 MHz, D2O): δ = 103.05, 102.88, 102.86, 102.81, 102.69, 102.19, 84.20, 75.98, 75.89, 75.70, 75.64, 75.56, 75.54, 75.50, 74.91, 74.87, 74.81, 74.57, 73.44, 73.06, 73.05, 73.03, 73.00, 72.83, 70.17, 69.60, 69.55, 69.44, 69.38, 69.37, 68.80, 68.74, 68.57, 68.52, 67.97, 60.69, 39.37, 28.18, 26.50, 23.24, 22.09, 20.07. HRMS (ESI): m/z [M + H]+ calcd for C41H74NO31: 1076.4239; found: 1076.4240.Nonasaccharide 1Prepared from 21, and purified over a Sephadex LH-20 column (H2O) as a white solid; yield: 29 mg (75%); [α]D 25 –43.78 (c 0.08, H2O). 1H NMR (400 MHz, D2O): δ = 4.64 (d, J = 8.0 Hz, 1 H), 4.44–4.37 (m, 7 H), 4.35 (d, J = 8.0 Hz, 1 H), 4.13–4.08 (m, 5 H), 3.88–3.66 (m, 13 H), 3.63–3.45 (m, 16 H), 3.41–3.10 (m, 22 H), 2.89 (t, J = 7.5 Hz, 2 H), 1.62–1.50 (m, 4 H), 1.39–1.29 (m, 2 H). 13C NMR (201 MHz, D2O): δ = 106.29, 106.27, 106.18, 106.10, 105.99, 105.82, 105.64, 105.49, 87.49, 81.81, 81.65, 79.28, 79.24, 78.99, 78.86, 78.83, 78.80, 78.73, 78.20, 78.19, 78.17, 78.11, 78.08, 78.03, 77.85, 77.46, 77.32, 76.73, 76.40, 76.34, 76.31, 76.29, 76.19, 76.12, 73.45, 72.85, 72.73, 72.71, 72.69, 72.67, 72.04, 71.93, 71.26, 71.11, 63.99, 63.83, 63.23, 63.15, 42.64, 31.47, 29.72, 28.28, 25.38. HRMS (ESI): m/z [M + H]+ calcd for C59H104NO46: 1562.5824; found: 1562.5826.