Direct α-Selective Glycosylations of Acetyl-Protected 2-Deoxy- and 2,6-Dideoxythioglycosides by Preactivation Protocol

Abstract

An efficient preactivation protocol for the highly α-stereo­selective glycosylation of 2-deoxy- and 2,6-dideoxysugars has been developed using acetyl-protected 2-deoxy- and 2,6-dideoxythioglycosides as glycosyl donors. The approach allows a wide range of glycosyl acceptors and donors to be used.

Key words

preactivation - α-stereoselective glycosylation - 2-deoxy­glycosides - 2,6-dideoxysugars - carbohydrate

References and Notes

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22

Typical Glycosylation Procedure
Triflic anhydride (11.0 µL, 0.061 mmol) was added to a stirred solution of p-methylphenyl 3,4,6-tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (1a, 30.0 mg, 0.076 mmol), benzenesulfinyl morpholine (BSM, 12.9 mg, 0.061 mmol), and 4 Å MS (350 mg, activated powder) in CH₂Cl₂ (3.0 mL) at -72 ˚C under nitrogen atmosphere. The reaction mixture was stirred for 10 min. After loss of 1a detected by TLC, a solution of methyl 3-O-benzyl-4,6-O-benzylidene-α-d-glucopyranoside (2a, 18.8 mg, 0.051 mmol) in CH₂Cl₂ (0.5 mL) was added dropwise to the reaction mixture. The mixture was stirred for 30 min, and the reaction was quenched by Et₃N (8.0 µL). The precipitate was filtered off, and the filtrate was concentrated. The residue was purified by column chromatography on silica gel (PE-EtOAc, 2.5:1) to give methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(3,4,6-tri-O-acetyl-2-deoxy-α-d-galactopyranosyl)-α-d-gluco-pyranoside (3a, 27.6 mg, 84% yield) as a foam. R _f  = 0.35 (PE-EtOAc, 1.5:1). ^¹H NMR (500 MHz, CDCl₃): δ = 7.50 (dd, 2 H, J = 2.0, 7.5 Hz), 7.40-7.33 (m, 7 H), 7.29-7.27 (m, 1 H), 5.60 (s, 1 H), 5.37 (ddd, 1 H, J = 3.0, 5.0, 12.5 Hz), 5.15 (d, 1 H, J = 3.0 Hz), 5.14 (d, 1 H, J = 3.5 Hz), 4.93 (d, 1 H, J = 10.5 Hz), 4.89 (d, 1 H, J = 3.5 Hz), 4.71 (d, 1 H, J = 10.5 Hz), 4.36 (t, 1 H, J = 6.5 Hz), 4.31 (dd, 1 H, J = 4.5, 10.0 Hz), 3.98 (t, 1 H, J = 9.5 Hz), 3.90 (dd, 1 H, J = 6.5, 11.0 Hz), 3.87-3.74 (m, 4 H), 3.65 (t, 1 H, J = 9.5 Hz), 3.43 (s, 3 H), 2.13-2.08 (m, 4 H), 2.00 (s, 3 H), 1.96-1.92 (m, 4 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 170.13, 170.23, 169.79, 138.06, 137.26, 128.96, 128.54, 128.47, 128.25, 127.86, 125.95, 101.27, 97.12, 94.10, 82.71, 76.85, 75.74, 73.45, 69.00, 66.61, 65.87, 62.25, 61.87, 55.23, 29.86, 20.81, 20.70. MS (ESI-TOF, positive): m/z = 667 [M + Na]⁺. Anal. Calcd for C₃₃H₄₀O₁₃: C, 61.48; H, 6.25. Found: C, 61.65; H, 6.40.