Ingrid 't Hart

85 Chemical synthesis of sulfoglycolipid analog SM1a-core3 4 H-Ar), 7.40 – 7.13 (18H, m, H-Ar), 7.10 – 7.05 (2H, m, H-Ar), 7.04 – 6.94 (3H, m, H-Ar), 5.47 – 5.38 (2H, m, H-1, GlcNAc-II; C H -C 6 H 5 ), 5.17 (2H, d, J = 13.3 Hz, CH 2 ), 4.81 (1H, d, J = 13.2 Hz, H-1, GalNAc-I), 4.68 (1H, d, J = 12.1 Hz, CH H ), 4.60 (1H, d, J = 11.6 Hz, CH H ), 4.57 – 4.43 (4H, m, CH H ; CH H ; CH 2 ), 4.38 (1H, d, J = 1.8 Hz, H-4, GalNAc-I), 4.33 – 4.26 (2H, m H-3, GlcNAc-II; H-2, GlcNAc-II), 4.10 (1H, d, J = 10.7 Hz, H-6a, GalNAc-I), 3.95 (1H, d, J = 9.8 Hz, H-3, GalNAc-I), 3.87 – 3.69 (5H, m, H-6, GlcNAc-II; H-6b, GalNAc-I; H-5, GlcNAc-II; H-4, GlcNAc-II), 3.61 – 3.44 (3H, m, H-2, GalNAc-I; CH H, pentyl; H-5, GalNAc-I), 3.39 – 3.10 (3H, m, CH H , pentyl, CH 2 , pentyl), 2.61 (1H, d, J = 10.4 Hz, O H ), 1.62 – 1.39 (4H, m, 2x CH 2 , pentyl), 1.32 – 1.12 (2H,m, J = 36.9, 11.8Hz, CH 2 , pentyl). 13 CNMR (151MHz, CDCl 3 ) δ138.0 (C=O, Cbz), 137.7 (C, NPhth), 133.7, 131.8, 128.6, 128.5, 128.3, 128.0, 127.9, 127.9, 127.8, 127.6, 126.1, 123.2, 100.4 ( C H-C 6 H 5 ) , 99.8 (C-1, GlcNAc-II), 98.4 (C-1, GalNAc-I), 79.0 (C- 3, GlcNAc-II), 75.8 (C-3, GalNAc-I), 75.5 (C-4, GalNAc-I), 74.3 (CH 2 ) , 73.8 (CH 2 ), 73.5 (C-5, GlcNAc-II), 71.0 (C-6, GlcNAc-II), 69.0 (C-6, GalNAc-I), 68.2 (CH 2 , pentyl), 67.1 (CH 2 ), 62.9 (C-5, GalNAc-I), 58.3 (C-2, GalNAc-I), 55.3 (C-2, GlcNAc-II), 29.0 (CH 2 , pentyl) 23.3 (CH 2 , pentyl). ESI HRMS (m/z): [M + Na] + calcd for C 61 H 63 N 5 O 13 ; 1096.4320 found 1096.4250. Phenyl 2- O -benzoyl-3- O -(2-naphthyl)methyl-4,6- O -benzylidene-1-thio-β-D-galacto- pyranoside (26). Compound 25 was synthesized as described before. 30 Benzoyl chloride (0.72 mL, 6.2 mmol) was added to a s�rring solu�on of compound 25 (2.08 g, 4.1 mmol) in pyridine (10 mL). A�er 1 h the mixture was concentrated in vacuo , separated between EtOAc/H 2 O, dried (Na 2 SO 4 ), filtered and the filtrate concentrated in vacuo . The obtained residue was dissolved in a small amount of DCM and crystallized by adding hexane. The resul�ng solids were filtered, collected and dried in high vacuo (1.99 g, 80 %). 1 H NMR (600 MHz, CDCl 3 ) δ 8.03 (2H, d, J = 7.7 Hz, H-Ar), 7.74 (1H, d, J = 7.8 Hz, H-Ar), 7.65 – 7.55 (4H, m, H-Ar), 7.53 – 7.34 (9H, m, H-Ar), 7.32 – 7.20 (6H, m, H-Ar), 5.59 (1H, t, J = 9.7 Hz, H-2), 5.49 (1H, s, C H -C 6 H 5 ), 4.82 – 4.76 (2H, m, CH H , Nap; H-1), 4.72 (1H, d, J = 13.0 Hz, CH H , Nap), 4.38 (1H, d, J = 12.1 Hz, H-6a), 4.28 (1H, s, H-4), 4.02 (1H, d, J = 12.1 Hz, H-6b), 3.81 (1H, d, J = 9.6 Hz, H-3), 3.49 (1H, s, H-5). 13 C NMR (151 MHz, CDCl 3 ) δ 133.8, 133.0, 129.9, 129.1, 128.7, 128.5, 128.4, 128.2, 128.0, 127.8, 127.7, 126.7, 126.5, 126.1, 126.0, 125.7, 101.3 ( C H-C 6 H 5 ), 85.4 (C-1), 78.1 (C-3), 73.2 (C-4), 71.1 (CH 2 ), 70.1 (C-5), 69.3 (C- 6), 69.0 (C-2). ESI HRMS (m/z): [M + NH] + calcd for C 37 H 32 O 6 S; 622.2263 found 622.2273. Phenyl 2- O -benzoyl-6- O -benzyl-3- O -(2-naphthyl)methyl-1-thio-β-D-galactopyranoside (27). Compound 26 (1.17 g, 1.9 mmol) was s�rred with 4 Å molecular sieves in DCM (20 mL) for 1 h. The mixture was cooled by an ice bath and Et 3 SiH (2.5 mL, 15.5 mmol) and TFA (0.89 mL, 11.6 mmol) were added. The progress of the reac�on was monitored by TLC (Toluene:EtOAc 9:1 v/v) and more reagents (2x 1.25 mL Et 3 SiH and 2 x 0.44 mL TFA) were added over �me (a�er 1 and 2 h) to drive the reac�on to comple�on. A�er s�rring overnight, H 2 O (4 mL) was added and the mixture was filtered. The filtrate was diluted with DCM, washed with sat. aq. NaHCO 3 , brine and the organic layer was dried (Na 2 SO 4 ), filtered and the filtrate concentrated in vacuo . The obtained residue was purified by silica column chromatography using Toluene:EtOAc (1:0 to 17:3 v/v) as the eluent to afford compound 27 (1.12 g, 95 %). 1H NMR (600 MHz, CDCl3) δ 7.97 (2H, d, J = 7.2 Hz, H-Ar), 7.71 (1H, d, J = 7.7 Hz, H-Ar), 7.61 – 7.55 (3H, m, H-Ar), 7.52 (1H, d, J = 8.4 Hz, H-Ar), 7.48 – 7.12 (15H, m, H-Ar), 5.52 (1H, t, J = 9.7 Hz, H-2), O O O NapO OBz SPh Ph O OBn HO NapO OBz SPh