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  •   S1  

    Supplementary Figure 1. Synthesis of galactofuranosyl building blocks 18–20.

    Regents and conditions: (a) TBSCl, imidazole, CH2Cl2, 0 °C, 66%; (b) BnBr, NaH,

    DMF, 0 °C to r.t., 81%; (c) TBAF, THF; (d) AcOH/H2O (7:3), 50 °C, 94% over two

    steps; (e) PhCH(OMe)2, PPTS, DMF, 60 °C, 85%; (f) DIBAL-H, CH2Cl2/Toluene

    (1:1), -40 °C, 88% (18f : 18g = 1 : 2.1); (g) Bz2O, DMAP, pyridine, 63%; (h) TBSCl,

    imidazole, CH2Cl2, 0 °C; (i) BzCl, DMAP, pyridine, 87% over two steps; (j)

    HF-pyridine, THF/H2O (10:1), 35 °C, 96%.

  •   S2  

    Supplementary Figure 2. MALDI-TOF mass spectra of 30-mer polysaccharide

    (22) before and after purification by size exclusion chromatography. a, Some

    deletion sequences were difficult to be removed by column chromatography on silica

    gel; b, All deletion sequences were removed by size exclusion chromatography to

    obtain the pure 30-mer polysaccharide (22).

  •   S3  

     

    Supplementary Figure 3. Synthesis of galactofuranosyl building block 24b.

    Regents and conditions: (a) TBAF, THF; (b) BzCl, DMAP, pyridine, 94% over two

    steps; (c) AcOH/H2O (7:3), 50 °C, 93%; (d) TBSCl, imidazole, CH2Cl2, 0 °C; (e)

    Levulinoyl acid, EDC·HCl, DMAP, CH2Cl2, 80% over two steps; (f) HF-pyridine,

    THF/H2O (10:1), 35 °C; (g) TBSCl, imidazole, CH2Cl2, reflux, 96%; (h) p-TolSCl,

    AgOTf, TTBP, then 24d, 4 Å MS, CH2Cl2, -78 °C, 55%; (i) Levulinoyl acid,

    EDC·HCl, DMAP, CH2Cl2, 35 °C; (j) HF-pyridine, THF/H2O (10:1), 35 °C, 74% over

    two steps.

  •   S4  

     

    Supplementary Figure 4. Synthesis of arabinofuranosyl building blocks 26, 27

    and 29. Regents and conditions: (a) CH3ONa, CH3OH; (b) Levulinoyl acid, EDC·HCl,

    DMAP, CH2Cl2, 86% for two steps; (c) AcBr, CH3OH, CH2Cl2, 0 °C to r.t.; (d)

    2,6-Lutidine, CH3OH, 0 °C to r.t.; (e) CH3ONa, CH3OH; (f) TBSCl, DMAP, Et3N,

    pyridine, 57% for four steps; (g) BnBr, NaH, DMF, 0 °C, 86%; (h) SnCl4, p-TolSH, 4

    Å MS, CH2Cl2, 0 °C, 62%; (i) TBAF, AcOH, THF, 35 °C, 92%.

  • S5  

    Supplementary Figure 5. 1H NMR spectrum of compound 18b

    OTBS

    HO O

    O

    O

    STol

    18b 

  • S6  

    Supplementary Figure 6. 13C NMR spectrum of compound 18b

    OTBS

    HO O

    O

    O

    STol

    18b 

  • S7  

    Supplementary Figure 7. 1H NMR spectrum of compound 18c

    18c 

  • S8  

    Supplementary Figure 8. 13C NMR spectrum of compound 18c

    18c 

  • S9  

    Supplementary Figure 9. 1H NMR spectrum of compound 18d

     

    18d 

  • S10  

    Supplementary Figure 10. 13C NMR spectrum of compound 18d

     

    18d 

  • S11  

    Supplementary Figure 11. 1H NMR spectrum of compound 18e

     

    18e 

  • S12  

    Supplementary Figure 12. 13C NMR spectrum of compound 18e

      18e 

  • S13  

    Supplementary Figure 13. 1H NMR spectrum of compound 18f

     

    18f 

  • S14  

    Supplementary Figure 14. 13C NMR spectrum of compound 18f

     

    18f 

  • S15  

    Supplementary Figure 15. 1H NMR spectrum of compound 18g

     

    18g 

  • S16  

    Supplementary Figure 16. 13C NMR spectrum of compound 18g

     

    18g 

  • S17  

    Supplementary Figure 17. 1H NMR spectrum of compound 18

     

    18 

  • S18  

    Supplementary Figure 18. 13C NMR spectrum of compound 18

    18 

  • S19  

    Supplementary Figure 19. 1H NMR spectrum of compound 19

     

    19 

  • S20  

    Supplementary Figure 20. 13C NMR spectrum of compound 19

     

    19 

  • S21  

    Supplementary Figure 21. 1H NMR spectrum of compound 20

     

    20 

  • S22  

    Supplementary Figure 22. 13C NMR spectrum of compound 20

      20 

  • S23  

    Supplementary Figure 23. 1H NMR spectrum of compound 8

    O

    OBz

    BnOO

    BnO

    O

    OBz

    BnOO

    TBSO BnO

    OBz

    BnOO BnO

    OBz

    BnOO

    BnO

    O

    STol

    2

     

  • S24  

    Supplementary Figure 24. 13C NMR spectrum of compound 8

  • S25  

    Supplementary Figure 25. COSY NMR spectrum of compound 8

  • S26  

    Supplementary Figure 26. HSQC NMR spectrum of compound 8

  • S27  

    Supplementary Figure 27. HMBC NMR spectrum of compound 8

  • S28  

    Supplementary Figure 28. 1H NMR spectrum of compound 5

    O

    OBz

    BnOO

    BnO

    O

    OBz

    BnOO

    HO BnO

    OBz

    BnOO BnO

    OBz

    BnOO

    BnO

    O

    STol

    2

  • S29  

    Supplementary Figure 29. 13C NMR spectrum of compound 5

    O

    OBz

    BnOO

    BnO

    O

    OBz

    BnOO

    HO BnO

    OBz

    BnOO BnO

    OBz

    BnOO

    BnO

    O

    STol

    2

  • S30  

    Supplementary Figure 30. 1H NMR spectrum of compound 4

  • S31  

    Supplementary Figure 31. 13C NMR spectrum of compound 4

  • S32  

    Supplementary Figure 32. 1H NMR spectrum of compound 21

    21 

  • S33  

    Supplementary Figure 33. 13C NMR spectrum of compound 21

     

    21 

  • S34  

    Supplementary Figure 34. 1H NMR spectrum of compound 6

    6

  • S35  

    Supplementary Figure 35. 13C NMR spectrum of compound 6

  • S36  

    Supplementary Figure 36. 1H NMR spectrum of compound 22

    22

  • S37  

    Supplementary Figure 37. 13C NMR spectrum of compound 22

      22

  • S38  

    Supplementary Figure 38. HSQC NMR spectrum of compound 22

  • S39  

    Supplementary Figure 39. MALDI-TOF MS spectrum of compound 22

    Calcd for C825H802O182Na [M + Na]+ m/z: 13652.1, found: 13650.8. 

    22

  • S40  

    Supplementary Figure 40. 1H NMR spectrum of compound 23

    O

    OH

    HOO

    HO

    O

    OH

    HOO

    HO HO

    OH

    HOO HO

    OH

    HOO

    HO

    O

    OC8H17

    14

    23

  • S41  

    Supplementary Figure 41. 13C NMR spectrum of compound 23

    O

    OH

    HOO

    HO

    O

    OH

    HOO

    HO HO

    OH

    HOO HO

    OH

    HOO

    HO

    O

    OC8H17

    14  

    23

  • S42  

    Supplementary Figure 42. MALDI-TOF MS spectrum of compound 23

    O

    OH

    HOO

    HO

    O

    OH

    HOO

    HO HO

    OH

    HOO HO

    OH

    HOO

    HO

    O

    OC8H17

    14  

    Calcd for C188H318O151Na [M + Na]+ m/z: 5017.4, found: 5018.1. 

    23

  • S43  

    Supplementary Figure 43. 1H NMR spectrum of compound 24c

    24c

  • S44  

    Supplementary Figure 44. 13C NMR spectrum of compound 24c

    24c

  • S45  

    Supplementary Figure 45. 1H NMR spectrum of compound 24d

      24d

  • S46  

    Supplementary Figure 46. 13C NMR spectrum of compound 24d

      24d

  • S47  

    Supplementary Figure 47. 1H NMR spectrum of compound 24e

      24e

  • S48  

    Supplementary Figure 48. 13C NMR spectrum of compound 24e

      24e

  • S49  

    Supplementary Figure 49. 1H NMR spectrum of compound 24f

      24f

  • S50  

    Supplementary Figure 50. 13C NMR spectrum of compound 24f

    24f

  • S51  

    Supplementary Figure 51. 1H NMR spectrum of compound 24g

    24g

  • S52  

    Supplementary Figure 52. 13C NMR spectrum of compound 24g

    24g

  • S53  

    Supplementary Figure 53. 1H NMR spectrum of compound 24b

    O

    OBz

    BnO O

    BnO

    HO

    OBz

    BnO O LevO

    STol

      24b

  • S54  

    Supplementary Figure 54. 13C NMR spectrum of compound 24b

    O

    OBz

    BnO O

    BnO

    HO

    OBz

    BnO O LevO

    STol

    24b

  • S55  

    Supplementary Figure 55. 1H NMR spectrum of compound 9

    O

    OBz

    BnOO

    BnO

    O

    OBz

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