One-Pot Assembly of Octasaccharide Motif from Cranberry Arabinoxyloglucan Oligosaccharides

Abstract

Chemical synthesis of octasaccharide motif from cranberry arabinoxyloglucan oligosaccharides with antiadhesion activities has been achieved for the first time. Synthetic approach highlights the following features: 1) stereoselective constructions of 1,2-cis-Xyl bonds via the combination of reagent modulation and remote participation; 2) modular [1+3+1+3] orthogonal one-pot assembly of the target octasaccharide on the basis of glycosyl ortho-(1-phenylvinyl)benzoate, which avoids the issues such as aglycone transfer associated with one-pot glycosylation based on thioglycosides.

Key words

cranberry - arabinoxyloglucan - chemical synthesis - 1,2-cis-xylosylation - one-pot glycosylation

Publication History

Received: 13 June 2024

Accepted after revision: 30 June 2024

Accepted Manuscript online:
30 June 2024

Article published online:
17 July 2024

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• 18 Procedure for Four-Component [1+3+1+3] Orthogonal One-Pot Synthesis of Octasaccharide 13 A suspension of glucosyl PTFAI 2 (56.0 mg, 0.07 mmol), glucosyl ABz acceptor 3 (79.8 mg, 0.07 mmol), and activated 4 Å MS (250 mg) in dry DCM (0.5 mL) was stirred at room temperature for 15 min under N₂ and was then cooled to 0 °C. A solution of HOTf in DCM (0.2 mL, 0.06 M) was slowly added to the mixture. After being stirred at 0 °C for another 2 h, the reaction mixture was warmed up to room temperature, to which glucosyl PVB acceptor 4 (36.7 mg, 0.06 mmol) in DCM (0.5 mL) and freshly prepared solution of Ph₃PAuOTf (1.0 mL, 0.012 M) were added successively. After being stirred for another 3 h, the reaction mixture was cooled to 0 °C, then the solution of acceptor 5 (70.7 mg, 0.05 mmol) in DCM (0.6 mL), NIS (18.5 mg, 0.08 mmol), and a solution of HOTf in DCM (0.2 mL, 0.08 M) were successively added. The resulting mixture was stirred at 0 °C to room temperature for another 4 h, then was quenched with Et₃N (0.5 mL) and filtered. The filtrates were concentrated under vacuum to give a residue, which was purified by flash column chromatography (PE/EtOAc = 5/1 to 3/1) to afford octasaccharide 13 (112.1 mg, 64% for one pot) as a white foam. [α]_D ²¹ +25.28 (c 0.11, CHCl₃). ¹H NMR (800 MHz, CDCl₃): δ = 8.18 (d, J = 7.2 Hz, 2 H, Ar), 8.03 (d, J = 8.0 Hz, 2 H, Ar), 8.01 (d, J = 8.0 Hz, 2 H, Ar), 7.98–7.97 (m, 4 H, Ar), 7.91 (d, J = 7.2 Hz, 2 H, Ar), 7.89 (d, J = 10.0 Hz, 2 H, Ar), 7.86–7.83 (m, 10 H, Ar), 7.79 (d, J = 7.2 Hz, 2 H, Ar), 7.62–7.59 (m, 3 H, Ar), 7.55–7.51 (m, 6 H, Ar), 7.48–7.45 (m, 3 H, Ar), 7.43–7.39 (m, 10 H, Ar), 7.37–7.36 (m, 4 H, Ar), 7.34–7.28 (m, 24 H, Ar), 7.26–7.24 (m, 7 H, Ar), 7.22–7.18 (m, 9 H, Ar), 7.16–7.14 (m, 5 H, Ar), 7.11–7.07 (m, 8 H, Ar), 7.00–6.98 (m, 1 H, Ar), 6.91–6.89 (m, 5 H, Ar), 6.87–6.85 (m, 2 H, Ar), 6.76–6.75 (m, 2 H, Ar), 6.15 (t, J = 9.6 Hz, 1 H), 5.84–5.79 (m, 3 H), 5.71 (t, J = 9.6 Hz, 1 H), 5.50 (s, 1 H), 5.46 (d, J = 5.6 Hz, 1 H), 5.44 (d, J = 4.8 Hz, 1 H), 5.41 (d, J = 8.0 Hz, 1 H), 5.38 (t, J = 8.8 Hz, 1 H), 5.32 (d, J = 8.8 Hz, 1 H), 5.20 (t, J = 8.8 Hz, 1 H), 5.14–5.11 (m, 3 H), 5.04–5.00 (m, 3 H), 4.86 (d, J = 12.0 Hz, 1 H), 4.78–4.73 (m, 2 H), 4.70 (d, J = 12.0 Hz, 1 H), 4.68–4.64 (m, 2 H), 4.63–4.61 (m, 2 H), 4.56–4.52 (m, 3 H), 4.50–4.49 (m, 2 H), 4.46–4.43 (m, 2 H), 4.37–4.32 (m, 4 H), 4.31–4.29 (m, 1 H), 4.20–4.18 (m, 2 H), 4.13 (d, J = 4.8 Hz, 1 H), 3.99 (d, J = 12.0 Hz, 1 H), 3.87–3.84 (m, 3 H), 3.81–3.74 (m, 4 H), 3.73–3.70 (m, 2 H), 3.66–3.63 (m, 3 H), 3.61–3.58 (m, 2 H), 3.57–3.54 (m, 3 H), 3.49 (d, J = 9.6 Hz, 1 H), 3.39 (t, J = 8.8 Hz, 1 H), 3.28–3.17 (m, 3 H), 2.95–2.82 (m, 2 H), 1.28–1.17 (m, 4 H), 0.97–0.92 (m, 3 H, CH₂). ¹³C NMR (151 MHz, CDCl₃): δ = 166.07, 166.04, 165.58, 165.56, 165.50, 165.32, 165.15, 165.12, 164.97, 164.92, 164.82, 164.49, 138.42, 138.31, 138.23, 138.09, 137.95, 137.83, 136.89, 134.14, 133.49, 133.36, 133.24, 133.20, 133.15, 133.09, 133.04, 132.98, 132.87, 132.78, 130.16, 130.12, 130.02, 129.99, 129.93, 129.83, 129.80, 129.75, 129.73, 129.66, 129.64, 129.56, 129.45, 129.08, 129.05, 128.96, 128.74, 128.62, 128.56, 128.53, 128.47, 128.44, 128.39, 128.35, 128.33, 128.29, 128.28, 128.24, 128.20, 128.17, 128.13, 127.95, 127.92, 127.88, 127.83, 127.81, 127.76, 127.70, 127.61, 127.47, 127.14, 127.10, 127.06, 127.01, 126.69, 103.08, 102.93, 101.07, 100.91, 100.76, 100.47, 96.20, 95.83, 82.63, 82.59, 80.98, 80.85, 80.48, 79.52, 78.60, 78.24, 77.49, 76.35, 75.38, 75.28, 75.16, 74.93, 74.80, 74.40, 74.13, 73.79, 73.53, 73.46, 73.37, 73.32, 73.27, 73.21, 72.90, 72.57, 72.30, 72.08, 72.02, 69.63, 67.75, 67.42, 66.98, 63.08, 62.90, 60.33, 59.67, 53.49, 50.44, 50.13, 47.13, 46.11, 31.97, 29.74, 29.70, 29.41, 28.99, 28.84, 27.59, 27.28, 23.03, 22.90, 22.74. MS (Maldi-TOF): m/z calcd for C₂₁₁H₁₉₃NO₅₄Na [M + Na]⁺: 3627.2279; found: 3627.2275.