Synlett, Table of Contents Synlett 2018; 29(05): 668-672DOI: 10.1055/s-0036-1591525 letter © Georg Thieme Verlag Stuttgart · New York Substoichiometric FeCl3 Activation of Propargyl Glycosides for the Synthesis of Disaccharides and Glycoconjugates Guosheng Sun a School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn , Yue Wu a School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn , Anqi Liu a School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn , Saifeng Qiu a School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. of China Email: Jbzhang@chem.ecnu.edu.cn , Wan Zhang 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, Northwest University, Xi’an, 710069, 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 Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract Glycosides as glycosyl donors using FeCl3 have been described. Under optimal reaction conditions, three kinds of propargyl glycosides were found to react with steroids and sugar-derived glycosyl acceptors to afford the corresponding disaccharides and glycoconjugates in good to excellent yields (66–91%). Meanwhile, the method can also realize one-pot synthesis of disaccharides, making it an effective, affordable, and green glycosylation procedure. Key words Key wordspropargyl glycosides - FeCl3 - disaccharides - glycoconjugates - glycosylation Full Text References References and Notes 1 Chiasson JL. Josse RG. Gomis R. Hanefeld M. Karasik A. Laakso M. Group S.-NT. R. Lancet 2002; 359: 2072 2 He BC. Gao JL. Luo X. Luo J. Shen J. Wang L. Zhou Q. Wang YT. Luu HH. Haydon RC. Wang CZ. Du W. Yuan CS. He TC. Zhang BQ. Int. J. Oncol. 2011; 38: 437 3 Mona MH. Omran NE. Mansoor MA. El-Fakharany ZM. Pharm. Biol. 2012; 50: 1144 4 Hamai S. J. Nanosci. Nanotechnol. 2001; 1: 177 5 Toole BP. Ghatak S. Misra S. Curr. Pharm. Biotechnol. 2008; 9: 249 6 Johnson MA. Cartmell J. Weisser NE. Woods RJ. Bundle DR. J. Biol. Chem. 2012; 287: 18078 7 Tsvetkov YE. Burg-Roderfeld M. Loers G. Arda A. Sukhova EV. Khatuntseva EA. Grachev AA. Chizhov AO. Siebert HC. Schachner M. Jimenez-Barbero J. Nifantiev NE. J. Am. Chem. Soc. 2012; 134: 426 8 Koeller KM. Wong CH. Chem. Rev. 2000; 100: 4465 9 Ragupathi G. Koide F. Livingston PO. Cho YS. Endo A. Wan Q. 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After completion of the reaction (monitored by TLC), the organic phase was condensed under vacuum to get crude product, which was purified by silica gel column chromatography (PE/EtOAc = 6:1) to get 3a in 83% yield. All new compounds were characterized by 1H NMR,13C NMR, and MS. Spectral and analytical data were in good agreement with the desired structures. 56 Selected Spectral Data – Compound 3a Colorless oil, α-anomer:1H NMR (500 MHz, CDCl3): δ = 8.00 (dd, J = 8.3, 1.2 Hz, 2 H), 7.97 (dd, J = 8.3, 1.2 Hz, 2 H), 7.91–7.85 (m, 2 H), 7.55–7.49 (m, 2 H), 7.46–7.28 (m, 24 H), 7.22 (m, 1 H), 7.15 (dd, J = 7.6, 1.7 Hz, 2 H), 6.16 (t, J = 9.4 Hz, 1 H), 5.55 (t, J = 9.9 Hz, 1 H), 5.24 (q, J = 3.5 Hz, 2 H), 4.93 (d, J = 11.0 Hz, 1 H), 4.84 (d, J = 11.0 Hz, 1 H), 4.80 (d, J = 11.0 Hz, 1 H), 4.78 (d, J = 12.5 Hz, 1 H), 4.76 (d, J = 3.5 Hz, 1 H), 4.65 (d, J = 12.2 Hz, 1 H), 4.56 (d, J = 12.1 Hz, 1 H), 4.47 (d, J = 11.0 Hz, 1 H), 4.40 (d, J = 12.1 Hz, 1 H), 4.36–4.31 (m, 1 H), 3.98 (t, J = 9.3 Hz, 1 H), 3.90–3.84 (m, 2 H), 3.67–3.62 (m, 2 H), 3.60 (dd, J = 11.0, 2.1 Hz, 1 H), 3.56 (dd, J = 9.7, 3.5 Hz, 1 H), 3.52 (dd, J = 10.7, 1.9 Hz, 1 H), 3.46 (s, 3 H). β-Anomer: 1H NMR (500 MHz, CDCl3): δ = 8.00–7.85 (m, 6 H), 7.52–7.12 (m, 29 H), 6.17 (t, J =9.8 Hz, 1 H), 5.47 (t, J =9.9 Hz, 1 H), 5.25 (dd, J =10.2, 3.6 Hz, 1 H), 5.20 (d, J =3.6 Hz, 1 H), 5.05 (d, J =10.8 Hz, 1 H), 4.91 (d, J =10.9 Hz, 1 H), 4.80 (d, J =10.8 Hz, 1 H), 4.76 (d, J = 10.9 Hz, 1 H), 4.68 (d, J =10.9 Hz, 1 H), 4.53 (d, J =11.5 Hz, 1 H), 4.50 (d, J =11.6 Hz, 1 H), 4.47 (d, J =7.8 Hz, 1 H), 4.43 (d, J =12.2 Hz, 1 H), 4.41–4.34 (m, 1 H), 4.12 (dd, J =10.8, 2.0 Hz, 1 H), 3.81 (dd, J = 10.9, 7.6 Hz, 1 H), 3.66–3.63 (m, 2 H), 3.61 (d, J = 6.0 Hz, 1 H), 3.58 (d, J = 9.1 Hz, 1 H), 3.46–3.43 (m, 2 H), 3.37 (s, 3 H). ESI-MS: m/z calcd for C62H60O14 Na [M + Na+]: 1051.39; found: 1051.25. Supplementary Material Supplementary Material Supporting Information
