Ingrid 't Hart

88 Chapter 4 4 (H 3 C-C =O, Lev), 172.0 (O- C =O, Lev), 165.0 (C=O, Bz), 138.6, 137.9, 137.8, 137.7, 134.8, 133.6, 133.3, 133.0, 133.0, 131.8, 129.9, 129.7, 128.5, 128.5, 128.3, 128.1, 128.0, 127.9, 127.8, 127.7, 127.6, 127.0, 126.9, 126.0, 123.2, 100.9 (C-1, Gal-III), 100.3 ( C H-C 6 H 5 ), 99.6 (C-1, GalNAc-I), 98.4 (C-1, GlcNAc-II), 78.3 (C-4, GlcNAc-II), 77.2 (C-3, GlcNAc-II), 76.2 (C- 3, Gal-III), 75.8 (C-3, GalNAc-I), 75.3 (C-4, GalNAc-I), 74.6 (CH 2 ), 74.3 (C-5, GlcNAc-II), 73.7 (CH 2 ), 73.4 (CH 2 ), 72.2 (C-5, Gal-III), 71.8 (C-2, Gal-III), 70.7 (CH 2 ), 68.9 (C-6, GalNAc-I), 68.8 (C-6, GlcNAc-II), 68.1 (CH 2 , pentyl), 67.5 (C-6, Gal-III) 67.1 (CH 2 ), 66.0 (C-4, Gal-III), 62.8 (C-5, GalNAc-I), 58.1 (C-2, GalNAc-I), 55.6 (C-2, GlcNAc-II), 50.6 (CH 2 ), 47.0 (CH 2 , pentyl) , 38.0 (CH 2 , Lev) , 29.7 (CH 3 , Lev), 28.0 (CH 2 , pentyl) , 27.4 (CH 2 , pentyl), 23.2 (CH 2 , pentyl). ESI HRMS (m/z): [M + NH] + calcd for C 97 H 97 N 5 O 21 ; 1685.7020 found 1685.7068. N -(Benzyl)-benzyloxycarbonyl-5-aminopentyl 2- O -benzoyl-6- O -benzyl-3- O - (2-naphthyl)methyl-β-D-galactopyranoside-(1→4)-3,6-di- O -benzyl-2-deoxy-2- phthalimido-β-D-glucopyranosyl-(1→3)-2-azido-4,6- O -benzylidene-2-deoxy-α-D- galactopyranoside (4). Hydrazine acetate (21 mg, 0.22 mg) was added to compound 14 (250 mg, 0.15 mmol) in DCM/MeOH (2/1 mL). The reac�on mixture was heated to 50 °C and s�rred overnight. A�er full conversion of the star�ng material was observed by MALDI-TOF, the mixture was concentrated in vacuo. The obtained residue was purified by silica column chromatography using Toluene:Acetone (1:0 to 9:1 v/v) as the eluent to afford compound 4 (212 mg, 90 %). 1 H NMR (600 MHz, CDCl 3 ) δ 7.92 (2H, d, J = 7.7 Hz, H-Ar), 7.73 (1H, d, J = 7.9 Hz, H-Ar), 7.69 – 6.91 (40H, m, H-Ar), 6.88 – 6.78 (3H, m, H-Ar), 5.54 – 5.50 (1H, m, H-2, Gal-III), 5.31 (1H, s, C H -C 6 H 5 ), 5.28 (1H, d, J = 8.2 Hz, H-1, GlcNAc-II), 5.15 (2H, d, J = 10.2 Hz, CH 2 ), 4.90 – 4.81 (2H, m, CH H ; CH H ), 4.74 (1H, d, J = 15.0 Hz, H-1, GalNAc-I), 4.65 – 4.57 (2H, m, H-1, Gal-III; CH H ), 4.51 – 4.41 (5H, m, CH 2 ; CH H ; CH 2 ), 4.35 (1H, t, J = 13.2 Hz, CH H ), 4.31 – 4.21 (3H, m, H-3, GlcNAc-II; H-4, GalNAc-I; H-2, GlcNAc-II), 4.19 (1H, d, J = 2.8 Hz, H-4, Gal-III), 4.07 – 3.98 (2H, m, CH H ; H-6a, GalNAc-I), 3.92 (1H, d, J = 7.7 Hz, H-4, GlcNAc-II), 3.84 (1H, s, H-3, GalNAc-I), 3.73 (1H, dd, J = 9.6, 6.7 Hz, H-6a, Gal-III), 3.63 – 3.43 (m, 9H, H-6, GlcNAc-II; H-6b, GalNAc-I; H-5, Gal-III; H-3, Gal-III; H-2, GalNAc-I; H-6b, Gal-III; H-5, GlcNAc-II; CH H , pentyl), 3.38 (1H, d, J = 26.2 Hz, H-5, GalNAc-I), 3.31 – 3.10 (3H, m, CH H , pentyl CH 2 , pentyl), 1.52 – 1.33 (4H, m, 2x CH 2 , pentyl), 1.30 – 1.08 (2H, m, CH 2 , pentyl). 13 C NMR (151 MHz, CDCl 3 ) δ 165.2 (C=O, Bz), 138.6, 138.0, 138.0, 137.7, 137.3, 134.6, 133.5, 133.3, 133.1, 131.8, 129.9, 129.8, 129.1, 128.6, 128.5, 128.5, 128.3, 128.0, 128.0, 127.9, 127.8, 127.8, 127.7, 127.7, 127.7, 127.2, 127.0, 126.9, 126.3, 126.1, 126.1, 125.8, 123.2, 100.9 (C-1, Gal-III), 100.3 ( C H-C 6 H 5 ), 99.6 (C-1, GlcNAc-II), 98.4 (C-1, GalNAc-I), 78.4 (C-4, GlcNAc-II), 78.1 (C-5, Gal-III), 77.3 (C-3, GlcNAc-II), 75.9 (C-3, GalNAc-I), 75.4 (C-4, GalNAc-I), 74.8 (CH 2 ), 74.4 (C-5, GlcNAc-II), 73.7 (CH 2 ), 73.4 (CH 2 ), 73.3 (C-3, Gal-III), 71.8 (C-2, Gal-III), 70.9 (CH 2 ), 69.0 (C-6, GalNAc-I), 69.0 (C-6, GlcNAc-II), 68.7 (C-6, Gal-III), 68.2 (CH 2 , pentyl), 67.2 (CH 2 ), 65.6 (C-4, Gal-III), 62.9 (C-5, GalNAc-I), 58.2 (C-2, GalNAc-I), 55.7 (C-2, GlcNAc-II), 50.6 (CH 2 ), 46.1 (CH 2 , pentyl), 29.0 (CH 2 , pentyl), 27.4 (CH 2 , pentyl), 23.2 (CH 2 , pentyl). ESI HRMS (m/z): [M + NH] + calcd for C 91 H 91 N 5 O 19 ; 1587.6652 found 1587.6690. O NPhth O BnO BnO O N 3 O O O O NBnCbz Ph O OBn HO NapO OBz