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

Publikationsverlauf

Eingereicht: 13. Juni 2024

Angenommen nach Revision: 30. Juni 2024

Accepted Manuscript online:
30. Juni 2024

Artikel online veröffentlicht:
17. Juli 2024

• References and Notes

• 1 Smith T, Kawa K, Eckl V, Stredney R. HerbalGram 2017; 115: 56
• 2a Blumberg JB, Basu A, Krueger CG, Lila MA, Neto CC, Novotny JA, Reed JD, Rodriguez-Mateos A, Toner CD. Adv. Nutr. 2016; 7: 759S
• 2b Alexander B, John S. J. Dent. Med. Sci. 2018; 18: 41
• 3 Avorn J, Monane M, Gurwitz JH, Glynn RJ, Choodnovskiy I, Lipsitz LA. JAMA, J. Am. Med. Assoc. 1994; 271: 751
• 4 Philip N, Walsh LJ. Dent. J. 2019; 7: 20
• 5 Kowalska K, Olejnik A. J. Funct. Foods 2016; 20: 171
• 6 Basu A. Nutrients 2019; 11: 1983
• 7 Neto C. Mol. Nutr. Food Res. 2007; 51: 652
• 8 Neto C. J. Nutr. 2007; 137: 186S
• 9a Coleman CM, Auker KM, Killday KB, Azadi P, Black I, Ferreira D. J. Nat. Prod. 2019; 82: 589
• 9b Coleman CM, Ferreira D. Molecules 2020; 25: 881
• 10 Auker KM, Coleman CM, Wang M, Avula B, Bonnet SL, Kimble LL, Mathison BD, Chew BP, Ferreira D. J. Nat. Prod. 2019; 82: 606
• 11a Nigudkar SS, Demchenko AV. Chem. Sci. 2015; 6: 2687
• 11b Dallabernardina P, Schuhmacher F, Seeberger PH, Pfrengle F. Org. Biomol. Chem. 2016; 14: 309
• 11c Tamura T, Omura Y, Tamura J. J. Org. Chem. 2020; 85: 12935
• 11d Cai D, Bian Y, Wu S, Ding K. J. Org. Chem. 2021; 86: 9945
• 11e Lei JC, Jiang YY, Xia YF, Fang Q, Duan SC, Ruan YX, Yang JS. Chin. J. Chem. 2022; 40: 1799
• 11f Li T, Zhang M, Lv P, Yang Y, Schmidt RR, Peng P. J. Org. Chem. 2024; 89: 804

For selective reviews, see:
• 12a Kulkarni SS, Wang C.-C, Sabbavarapu NM, Podilapu AR, Liao P.-H, Hung S.-C. Chem. Rev. 2018; 118: 8025
• 12b Cheng CW, Wu CY, Hsu WL, Wong CH. Biochemistry 2020; 59: 3078
• 12c Wang X, Xiao G. Curr. Opin. Chem. Biol. 2023; 77: 102387
• 12d Wang X, Xiao G. ChemBioChem 2023; 24: e202300552
• 13a Li P, He H, Zhang Y, Yang R, Xu L, Chen Z, Huang Y, Bao L, Xiao G. Nat. Commun. 2020; 11: 405
• 13b He H, Xu L, Sun R, Zhang Y, Huang Y, Chen Z, Li P, Yang R, Xiao G. Chem. Sci. 2021; 12: 5143
• 14a Ma Y, Zhang Y, Huang Y, Chen Z, Xian Q, Su R, Jiang Q, Wang X, Xiao G. J. Am. Chem. Soc. 2024; 146: 4112
• 14b Zhang Y, Wang L, Zhou Q, Li Z, Li D, Yin C, Wang X, Xiao G. Angew. Chem. Int. Ed. 2023; 62: e202301351
• 14c Zhang Y, He H, Chen Z, Huang Y, Xiang G, Li P, Yang X, Lu G, Xiao G. Angew. Chem. Int. Ed. 2021; 60: 12597
• 14d Zhang Y, Chen Z, Huang Y, He S, Yang X, Wu Z, Wang X, Xiao G. Angew. Chem. Int. Ed. 2020; 59: 7576
• 14e Zhang Y, Hu Y, Liu S, He H, Sun R, Lu G, Xiao G. Chem. Sci. 2022; 13: 7755
• 14f Shou K, Zhang Y, Ji Y, Liu B, Zhou Q, Tan Q, Li F, Wang X, Lu G, Xiao G. Chem. Sci. 2024; 15: 6552
• 14g Shou K, Liu S, Zhang Y, Xiao G. Chin. J. Chem. 2024;  42: 1593
• 14h Ma Y, Jiang Q, Wang X, Xiao G. Org. Lett. 2022; 24: 7950
• 14i Sun X, Chen Z, Yang R, Wang M, Wang X, Zhang Q, Xiao G. Org. Lett. 2023; 25: 7364
• 14j Chen Z, Xiao G. Org. Lett. 2023; 25: 7395
• 14k Chen Z, Xiao G. J. Am. Chem. Soc. 2024; 146: 17446
• 15a Yu B, Sun J. Chem. Commun. 2010; 46: 4668
• 15b Yu B, Tao H. Tetrahedron Lett. 2001; 42: 2405
• 16a Li Y, Yang Y, Yu B. Tetrahedron Lett. 2008; 49: 3604
• 16b Yu B. Acc. Chem. Res. 2018; 51: 507
• 17 Horlacher T, Seeberger PH. Chem. Soc. Rev. 2008; 37: 1414
• 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.