Copper-Catalyzed Stereoselective Synthesis of 2-Deoxygalactosides

Youxian Dong; Madina Yuma; Yuling Mei; Nan Jiang; Guofang Yang; Zhongfu Wang; Jianbo Zhang

doi:10.1055/s-0040-1707098

Synlett, Table of Contents

Synlett 2020; 31(11): 1087-1093
DOI: 10.1055/s-0040-1707098

letter

Copper-Catalyzed Stereoselective Synthesis of 2-Deoxygalactosides

Youxian Dong

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

,

Madina Yuma

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

,

Yuling Mei

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

,

Nan Jiang

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

,

Guofang Yang

^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, Northwestern University, Xian 710069, Shaanxi, 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

› Author Affiliations

Abstract

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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

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References

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.

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