Ingrid 't Hart

71 Synthesis of globo-series glycolipids 3 (2S,3R,4E)-3-hydroxy-2-(hexadecanamido)octadec-4-enyl 2-acetamido-2-deoxy-β-D- galactopyranosyl-(1 → 3)-α-D-galactopyranosyl-(1 → 4)-β-D-galactopyranosyl-(1 → 4)-β- D-glucopyranoside (2b). Compound 2b was synthesized from compound 2a according to the general procedure for ceramide synthesis. The crude was purified by a 1mL C18 cartridge using H 2 O: CH 3 CN (1:0 to 0:1 v/v) as the eluent. The organic solvent was removed under N 2 flow and the residual water was removed by lyophiliza�on. (0.1 mg, 10%) 1 H NMR (600 MHz, MeOD) δ 5.72 – 5.63 (1H, m, CH=C H -CH 2 ), 5.44 (1H, dd, J = 15.3, 7.9 Hz, HOCH-C H =CH), 4.93 (1H, d, J = 3.9 Hz, H-1, Gal-III), 4.61 (1H, d, J = 9.0 Hz, H-1, GalNAc-IV), 4.43 – 4.38 (1H, m, H-1, Gal-II), 4.29 (1H, d, J = 7.8 Hz, H-1, Glc-I), 4.28 – 4.23 (1H, m), 4.16 (2H, dd, J = 9.3, 5.1 Hz), 4.08 – 4.04 (1H, m, HOC H -CH=CH), 3.99 – 3.23 (24H, m), 2.22 – 2.13 (2H, m, CH 2 , Cer), 2.05 – 1.97 (5H, m, J = 16.6 Hz, CH 2 , Cer; CH 3 , NHAc), 1.63 – 1.53 (2H, m, CH 2 , Cer), 1.43 – 1.20 (46H, m, 23 x CH 2 , Cer), 0.89 (6H, t, J = 6.7 Hz, 2 x CH 3 , Cer). ESI HRMS ( m/z ): [M + H] + calcd for C 60 H 110 N 2 O 23 ; 1227.7572 found 1227.7580. (2S,3R,4E)-3-hydroxy-2-(hexadecanamido)octadec-4-enyl β-D-galactopyranosyl- (1 → 3)-2-acetamido-2-deoxy-β-D-galactopyranosyl-(1 → 3)-α-D-galactopyranosyl- (1 → 4)-β-D-galactopyranosyl-(1 → 4)-β-D-glucopyranoside ( 3b ). Compound 3b was synthesized from compound 3a according to the general procedure for ceramide synthesis. The crude was purified by a 1mL C4 cartridge using H 2 O:MeOH (1:0 to 0:1 v/v) as the eluent. The organic solvent was removed under N 2 flowand the residual water was removed by lyophiliza�on. (0.2 mg, 29%) 1 H NMR (600 MHz, MeOD) δ 5.68 (1H, dd, J = 14.4, 7.2 Hz, CH=C H -CH 2 ), 5.44 (1H, dd, J = 14.7, 7.4 Hz, HOCH-C H =CH), 4.93 (1H, d, J = 3.3 Hz, H-1, Gal-III), 4.70 (1H, d, J = 8.5 Hz, H-1, GalNAc-IV), 4.42 – 4.38 (1H, m, H-1, Gal-II), 4.33 (1H, d, J = 7.4 Hz, H-1, Gal-V), 4.29 (1H, d, J = 7.6 Hz, H-1, Glc-I), 4.27 – 4.22 (1H, m), 4.19 – 3.24 (33H, m), 2.24 – 2.17 (2H, m, CH 2 , Cer), 2.06 – 1.95 (2H, m, CH 2 , Cer), 1.91 (3H, s, CH 3 , NHAc), 1.66 – 1.55 (2H, m, CH 2 , Cer), 1.43 – 1.21 (46H, m, 23 x CH 2 , Cer), 0.89 (6H, t, J = 7.0 Hz, 2 x CH 3 , Cer). ESI HRMS ( m/z ): [M + H] + calcd for C 66 H 120 N 2 O 28 ; 1389.8100 found 1389.8138. O HO OH HO AcHN O HO OH O HO O O OH HO OH O O OH HO OH HN OH C 13 H 27 O C 15 H 31 O O HO OH O AcHN O HO OH O HO O O OH HO OH O O OH HO OH HN OH C 13 H 27 O O C 15 H 31 O HO OH HO HO