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Synlett 2020; 31(11): 1087-1093
DOI: 10.1055/s-0040-1707098
DOI: 10.1055/s-0040-1707098
letter
Copper-Catalyzed Stereoselective Synthesis of 2-Deoxygalactosides
The project was financially supported by Natural Science Foundation of Shanghai (11ZR1410400) and by the Large Instruments Open Foundation of East China Normal University (20162015).
Further Information
Publication History
Received: 14 January 2020
Accepted after revision: 03 April 2020
Publication Date:
05 May 2020 (online)
Abstract
An efficient glycosylation method to synthesize 2-deoxy-O-galactosides based on a Cu(II)-catalyzed reaction without additional ligand has been developed. The glycosylation was amenable to different protected glycal donors and a wide range of acceptors including alcohols, amino acids, sugars, and phenol, and proceeds with excellent yield and high α-selectivity under mild conditions. The reaction proceeds readily on a gram scale, and its versatility is exemplified in the synthesis of oligosaccharides.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707098.
- Supporting Information
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References and Notes
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- 27 6-O-(3’,4’,6’-Tri-O-benzyl-2’-deoxy-α-d-galactopyranosyl)-1,2:3,4-di-O-isopropylidene-α-d-galactopyranoside (3g)Under a nitrogen atmosphere, glycal donor 1a (0.10 mmol, 41.6 mg) and nucleophile acceptor 2g (0.12 mmol, 31.2 mg) were dissolved in anhydrous DCM (1.0 mL). Meanwhile CuBr2 (0.005 mmol, 1.3 mg) was added to the system quickly. The reaction mixture was stirred at 25 °C until the reaction was determined to be complete by TLC. The reaction was then quenched with sat. aq. NaHCO3, and the mixture was extracted with DCM. The combined organic phases were washed with sat. aq. NaHCO3 and brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (PE/EtOAc = 6:1) to give a yellow syrup. Yield: 55.4 mg (82%), α:β >30:1. Trichloroethyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3c) Yield: 46.2 mg (82%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.39–7.26 (m, 15 H), 5.24 (d, J = 2.3 Hz, 1 H), 4.95 (d, J = 11.6 Hz, 1 H), 4.62 (d, J = 11.4 Hz, 3 H), 4.51 (d, J = 11.8 Hz, 1 H), 4.44 (d, J = 11.8 Hz, 1 H), 4.19 (d, J = 11.5 Hz, 1 H), 4.07 (d, J = 11.5 Hz, 1 H), 4.04–3.98 (m, 2 H), 3.96 (s, 1 H), 3.59 (d, J = 6.3 Hz, 2 H), 2.29 (td, J = 12.5, 3.4 Hz, 1 H), 2.16 (dd, J = 12.7, 4.2 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 138.81, 138.39, 138.09, 128.52, 128.50, 128.34, 128.34, 127.82, 127.70, 127.68, 127.53, 98.87, 96.85, 79.15, 74.43, 73.55, 72.90, 71.03, 70.69, 69.46, 30.73. HRMS (ESI): m/z [M + Na]+ calcd for C29H31Cl3NaO5: 587.1129; found: 587.1110. Furfuraldehyde-5-methyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3e) Yield: 48.2 mg (89%); yellow syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 9.61 (s, 1 H), 7.36–7.26 (m, 15 H), 7.17 (d, J = 3.5 Hz, 1 H), 6.48 (d, J = 3.5 Hz, 1 H), 5.08 (d, J = 3.1 Hz, 1 H), 4.94 (d, J = 11.6 Hz, 1 H), 4.66–4.58 (m, 4 H), 4.56–4.42 (m, 3 H), 3.96–3.90 (m, 3 H), 3.61–3.54 (m, 2 H), 2.26 (td, J = 12.6, 3.6 Hz, 1 H), 2.04 (dd, J = 12.8, 4.3 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 177.84, 157.96, 152.84, 138.85, 138.51, 138.11, 128.49, 128.31, 127.88, 127.81, 127.63, 127.37, 111.63, 97.69, 74.60, 74.39, 73.58, 72.93, 70.58, 70.48, 69.59, 60.96, 30.93. HRMS (ESI): m/z [M + Na]+ calcd for C33H34NaO7: 565.2197; found: 565.2196. N-(9-fluorenylmethoxycarbonyl)-L-serine methyl ester-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3f)Yield: 70.4 mg (93%); yellow syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.76 (d, J = 7.6 Hz, 2 H), 7.58 (d, J = 7.4 Hz, 2 H), 7.41–7.26 (m, 19 H), 5.91 (d, J = 8.7 Hz, 1 H), 4.94 (dd, J = 14.2, 7.0 Hz, 2 H), 4.64–4.56 (m, 3 H), 4.56–4.45 (m, 2 H), 4.43–4.32 (m, 3 H), 4.21 (t, J = 7.1 Hz, 1 H), 3.99 (dd, J = 10.8, 3.7 Hz, 1 H), 3.93–3.83 (m, 4 H), 3.75 (s, 3 H), 3.62–3.57 (m, 1 H), 3.56–3.51 (m, 1 H), 2.23 (td, J = 12.4, 3.4 Hz, 1 H), 1.96 (dd, J = 12.5, 3.9 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 170.81, 156.09, 143.91, 141.36, 138.79, 138.40, 138.03, 128.60, 128.21, 128.05, 127.53, 127.46, 127.13, 125.19, 120.04, 99.22, 74.38, 73.49, 72.82, 70.55, 69.58, 68.77, 67.18, 54.56, 52.63, 47.19, 31.12. HRMS (ESI): m/z [M + Na]+ calcd for C46H47NNaO9: 780.3143; found: 780.3127. 4-t-Butyl-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3k) Yield: 47.0 mg (83%); yellow syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.41–7.26 (m, 15 H), 7.24 (d, J = 7.2 Hz, 2 H), 7.00 (d, J = 8.7 Hz, 2 H), 5.69 (d, J = 2.9 Hz, 1 H), 4.98 (d, J = 11.5 Hz, 1 H), 4.70–4.64 (m, 3 H), 4.43 (d, J = 11.6 Hz, 1 H), 4.37 (d, J = 11.6 Hz, 1 H), 4.15 (dd, J = 11.1, 3.2 Hz, 1 H), 4.09 (t, J = 6.5 Hz, 1 H), 4.03 (s, 1 H), 3.70–3.64 (m, 1 H), 3.56 (dd, J = 9.3, 5.7 Hz, 1 H), 2.40 (td, J = 12.4, 3.6 Hz, 1 H), 2.21 (dd, J = 12.7, 4.4 Hz, 1 H), 1.30 (s, 9 H). 13C NMR (125 MHz, CDCl3): δ = 154.83, 144.65, 138.92, 138.57, 138.15, 128.52, 128.39, 128.3, 127.85, 127.69, 127.66, 127.62, 127.43, 126.26, 116.15, 96.82, 74.73, 74.51, 73.42, 72.98, 70.65, 69.32, 34.21, 31.59, 31.43. HRMS (ESI): m/z [M + Na]+ calcd for C37H42NaO5: 589.2924; found: 589.2916. 4-Fluoro-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3m) Yield: 41.7 mg (79%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.42–7.19 (m, 15 H), 7.01 (dd, J = 8.7, 4.4 Hz, 2 H), 6.93 (t, J = 8.5 Hz, 2 H), 5.62 (s, 1 H), 4.97 (d, J = 11.5 Hz, 1 H), 4.71–4.61 (m, 3 H), 4.43 (d, J = 11.6 Hz, 1 H), 4.37 (d, J = 11.6 Hz, 1 H), 4.12 (d, J = 11.6 Hz, 1 H), 4.04 (dd, J = 15.5, 9.2 Hz, 2 H), 3.67–3.60 (m, 1 H), 3.55 (dd, J = 9.2, 6.1 Hz, 1 H), 2.39 (dd, J = 12.4, 3.1 Hz, 1 H), 2.20 (dd, J = 12.7, 4.1 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 159.05, 157.14, 153.08, 138.83, 138.48, 138.06, 128.55, 128.43, 128.36, 128.32, 127.79, 127.77, 127.72, 127.68, 127.44, 118.14, 118.08, 115.94, 115.76, 97.36, 74.56, 74.51, 73.45, 72.93, 70.80, 70.66, 69.40, 31.31. HRMS (ESI): m/z [M + Na]+ calcd for C33H33FNaO5: 551.2204; found: 551.2194. 4-Chloro-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3n) Yield: 45.8 mg (75%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.41–7.19 (m, 17 H), 6.99 (t, J = 6.1 Hz, 2 H), 5.66 (d, J = 3.0 Hz, 1 H), 4.97 (d, J = 11.5 Hz, 1 H), 4.70–4.62 (m, 3 H), 4.41 (d, J = 11.6 Hz, 1 H), 4.36 (d, J = 11.6 Hz, 1 H), 4.10 (ddd, J = 11.9, 4.3, 2.3 Hz, 1 H), 4.03–3.97 (m, 2 H), 3.63 (dd, J = 9.3, 7.2 Hz, 1 H), 3.52 (dd, J = 9.4, 5.8 Hz, 1 H), 2.40 (td, J = 12.5, 3.6 Hz, 1 H), 2.20 (dd, J = 12.8, 4.5 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 155.51, 138.81, 138.45, 138.01, 129.40, 128.56, 128.44, 128.36, 128.31, 127.81, 127.78, 127.74, 127.69, 127.44, 126.94, 118.05, 96.86, 74.53, 74.50, 73.44, 72.86, 70.87, 70.67, 69.29, 31.20, 29.79. HRMS (ESI): m/z[M + Na]+ calcd for C33H33ClNaO5: 567.1909; found: 567.1895. 2-Methyl-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3p) Yield: 39.8 mg (76%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.41–7.20 (m, 15 H), 7.15–7.08 (m, 3 H), 6.94–6.86 (m, 1 H), 5.71 (d, J = 1.9 Hz, 1 H), 4.99 (d, J = 11.5 Hz, 1 H), 4.73–4.62 (m, 3 H), 4.42 (d, J = 11.6 Hz, 1 H), 4.36 (d, J = 11.6 Hz, 1 H), 4.18–4.11 (m, 1 H), 4.03 (d, J = 7.6 Hz, 2 H), 3.67 (t, J = 8.4 Hz, 1 H), 3.53 (dd, J = 9.2, 5.5 Hz, 1 H), 2.42 (td, J = 12.5, 3.4 Hz, 1 H), 2.22–2.18 (m, 1 H), 2.17 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 154.98, 138.92, 138.37, 138.05, 130.69, 128.53, 128.41, 128.33, 128.30, 127.89, 127.74, 127.73, 127.62, 127.15, 126.95, 121.58, 114.24, 96.28, 74.51, 74.28, 73.47, 72.96, 70.78, 70.53, 69.18, 31.50, 16.3. HRMS (ESI): m/z [M + Na]+ calcd for C34H36NaO5: 547.2455; found: 547.2441.