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Synlett 2020; 31(11): 1087-1093
DOI: 10.1055/s-0040-1707098
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Stereoselective Synthesis of 2-Deoxygalactosides

Youxian Dong
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, P. R. of China   Email: jbzhang@chem.ecnu.edu.cn
,
Madina Yuma
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, P. R. of China   Email: jbzhang@chem.ecnu.edu.cn
,
Yuling Mei
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, P. R. of China   Email: jbzhang@chem.ecnu.edu.cn
,
Nan Jiang
a   School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, P. R. of China   Email: jbzhang@chem.ecnu.edu.cn
,
Guofang Yang
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, Northwestern University, Xian 710069, Shaanxi, 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 AffiliationsThe 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)

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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.

Key words

copper catalyst - 2-deoxygalactosides - glycosylation - ­glycals - stereoselectivity

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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  • 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.