Supporting information for Highly Stereoselective Synthesis of Primary, Secondary and Tertiary -S-Sialosides under Lewis Acidic Conditions Amandine Noel, Bernard Delpech and David Crich * Centre de Recherche de Gif, Institut de Chimie des Substances Naturelles, CNRS, 1 Avenue de la Terrasse, 91190 Gif-sur-Yvette, France, and b) Department of Chemistry, Wayne State University, Detroit, MI 48202, USA S1
Compound Expt Spectra Methyl 6-O-triphenylmethyl-α-D-galactopyranoside (22) S4 S16-17 Methyl 2,3,4-tri-O-benzyl- -D-galactopyranoside (1). S4 S18-19 Methyl 2,3,4-tri-O-benzyl-6-acetylthio- -D-galactopyranoside (2) S5 S20-21 Methyl 2,3,4-tri-O-benzyl-6-thio- -D-galactopyranoside (3) S6 S22-23 Methyl 4,6-O-benzylidene-2-O-benzoyl-β-D-gulopyranoside (5) S6 - Methyl 4,6-O-benzylidene-2-O-benzoyl-3-thioacetyl-β-D-galactopyranoside (6) S6 S24-25 Methyl 4,6-O-benzylidene-2-O-benzoyl-3-thio-β-D-galactopyranoside (7) S7 S26-27 Methyl 2,3,6-tri-O-benzyl-4-acetylthio- -D-galactopyranoside (9) S7 S28-29 Methyl 2,3,6-tri-O-benzyl-4-thio- -D-galactopyranoside (10) S8 S30-31 Methyl (5-acetamido-2-benzylthio-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5- dideoxy-d-glycero- -D-galacto-non-2-ulopyranoside)onate (12) S9 S32-33 Methyl (5-acetamido-2-benzylthio-7,8,9-tri-O-acetyl-3,5-dideoxy-D-glyceroβ-D-galacto-non-2-ulopyranoside)onate (13) S9 S34-35 Methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-2-(4- methoxyphenyl)thio-d-glycero- -D-galacto-non-2-ulopyranoside)onate (14) S10 S36-37 Methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-2- tert-butylthio-d-glycero- -D-galacto-non-2-ulopyranoside)onate (15) S10 S38-39 Methyl (2-S-(methyl 2,3,4-tri-O-benzyl-6-thio- -D-galactopyranoside)-5-Nacetyl-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero- -Dgalacto-non-2-ulopyranoside)onate S11 S40-41 (16) Methyl (2-S-(methyl 4,6-O-benzylidene-2-O-benzoyl-3-thio-β-D- galactothiopyranoside)-5-n-acetyl-7,8,9-tri-o-acetyl-5-n,4-o-carbonyl-3,5- S12 S42-43 dideoxy-d-glycero- -D-galacto-non-2-ulopyranoside)onate (17) Methyl (2-S-(methyl 2,3,6-tri-O-benzyl-4-thio- -D-galactopyranoside)-5-Nacetyl-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero- -Dgalacto-non-2-ulopyranoside)onate S12 S44-45 (18) Methyl (2-S-(methyl 2,3,4-tri-O-benzyl-6-thio- -D-galactopyranoside)-5-Nacetyl-3,5-dideoxy-D-glycero- -D-galacto-non-2-ulopyranoside)onate (19) S13 S46-47 (2-S-(Methyl β-d-galactothiopyranoside)-5-n-acetyl-3,5-dideoxy-d-glyceroα-d-galacto-non-2-ulopyranoside)onic acid (20) S14 S48-49 Methyl (2-S-(methyl 2,3,6-tri-O-benzyl-4-thio- -D-galactopyranoside)-5-Nacetyl-3,5-dideoxy-D-glycero- -D-galacto-non-2-ulopyranoside)onate (21) S14 S50-51 S2
Reactions were performed using oven dried glasswares under an atmosphere of argon. All separations were carried out under flash-chromatographic conditions on silica gel (Redi Sep prepacked column, 230 400 mesh) at medium pressure (20 psi) with use of a CombiFlash Companion. Reactions were monitored by thin-layer chromatography on Merck silica gel plates (60 F 254 aluminum sheets) which were rendered visible by ultraviolet light and/or spraying with phosphomolybdic acid (10%) in EtOH or vanillin (15%) + sulfuric acid (2.5%) in EtOH followed by heating. CH 3 CN, THF, DMF, CH 2 Cl 2 and MeOH were purchased from Acros Organics at the highest commercial quality and used without further purification. Reagent-grade chemicals were obtained from diverse commercial suppliers (Sigma-Aldrich, Acros Organics, TCI and Alfa-Aesar) and were used as received. 1 H NMR (500 or 300 MHz) and 13 C NMR (125 or 75 MHz) spectra were recorded on Bruker Avance spectrometers at 298 K unless otherwise stated. Chemical shifts are given in (δ) and are referenced to the internal solvent signal or to TMS used as an internal standard. Multiplicities are declared as follow: s (singlet), br s (broad singlet), d (doublet), t (triplet), q (quadruplet), dd (doublet of doublet), ddd (doublet of doublet of doublet), dt (doublet of triplet), m (multiplet). Coupling constants J are given in Hz. Carbon multiplicities were determined by DEPT135 experiment. Diagnostic correlations were obtained by twodimensional COSY, HSQC and HMBC experiments. Infrared spectra (IR) were recorded on a Perkin-Elmer FT-IR system using diamond window Dura SamplIR II and the data are reported in reciprocal centimeters (cm -1 ). Optical rotations were measured on a Anton Paar MCP 300 polarimeter at 589 nm. [ ] t C D is expressed in deg.cm 3.g -1.dm -1 and c is expressed in g/100 cm 3. Melting points were recorded in open capillary tubes on a Büchi B-540 apparatus and are uncorrected. High resolution mass spectra (HRMS) were recorded using a Micromass LCT Premier XE instrument (Waters) and were determined by electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI). S3
Methyl 2,3,4-Tri-O-benzyl- -D-galactopyranoside (1). Methyl 6-O-triphenylmethyl-α-D-galactopyranoside (22). To a solution of methyl- -Dgalactopyranoside (2 g, 10.3 mmol) in CH 2 Cl 2 (40 ml), were added DABCO (2.3 g, 20.5 mmol), followed by 96% TrCl (6.0 g, 20.6 mmol). The reaction mixture was stirred at room temperature for 4 h. The solvent was removed under vacuum. After purification on a silica cartridge (CH 2 Cl 2 /MeOH 9:1), the desired product was obtained as a white solid (4.0 g, 90%). Mp = 80-82 C; [α] 20 D = 67.21 (c 4.3, CHCl 3 ); IR υ max (cm -1 ): 3409; 1 H NMR (300 MHz, CDCl 3 ): δ 7.50-7.19 (m, 15 H), 4.74 (d, J = 3.3 Hz, 1 H), 4.41 (br s, 1 H), 3.89 (br s, 1 H), 3.78-3.86 (m, 2 H), 3.66-3.76 (m, 2 H), 3.44 (dd, J = 9.8, 6.6 Hz, 1 H), 3.39 (s, 3 H), 3.34 (br s, 1 H), 3.30 (dd, J = 9.8, 5.3 Hz, 1 H); 13 C NMR (75 MHz, CDCl 3 ): δ 143.8 (3 C, C), 128.6 (6 C, CH), 127.8 (6 C, CH), 127.0 (3 C, CH), 99.4 (CH), 86.8 (C), 70.7 (CH), 69.9 (CH), 69.3, 69.2 (2 C, CH), 63.3 (CH 2 ), 55.1 (CH 3 ); MS (ESI + ) m/z (%) 459.2 (50, [M+Na] + ), 895.4 (100, [2M+Na] + ); ESIHRMS calcd for C 26 H 28 NaO 6 (M+Na) 459.1800, found 459.1784. Methyl 2,3,4-tri-O-benzyl- -D-galactopyranoside (1). To a solution of compound 22 (4.34 g, 9.94 mmol) in anhydrous DMF (38.2 ml), were added NaH 60% (3.2 g, 80.5 mmol), followed by benzyl bromide (7.1 ml, 59.7 mmol) and the reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with water and extracted with MTBE (methyl tert-butyl ether). The organic layer was washed with water, dried over Na 2 SO 4 and concentrated under vacuum. To a solution of the crude product in CH 2 Cl 2 (115 ml) were added at 0 C, Et 3 SiH (1.9 ml, 11.9 mmol) and TFA (4.7 ml) and the reaction mixture was stirred at this temperature for 1 h 30. The organic layer was washed with a saturated solution of NaHCO 3, extracted with CH 2 Cl 2, dried over Na 2 SO 4 and concentrated under vacuum. After purification on a silica cartridge (50:50 Heptane/AcOEt), the desired product was obtained as a colorless oil (3.31 g, 72%). [α] 20 D = 7.16 (c 1.9, CHCl 3 ); IR υ max (cm -1 ): 3474, 2902; 1 H NMR (300 MHz, CDCl 3 ): δ 7.24-7.47 (m, 15 H), 4.98 (d, J = 11.6 Hz, 1 H), 4.90 (d, J = 11.9 Hz, 1 H), 4.85 (d, J = 12.1 Hz, 1 H), 4.76 (d, J = 11.9 Hz, 1 H), 4.72 (d, J = 3.9 Hz, 1 H), 4.70 (d, J = 12.1 Hz, 1 H), 4.65 (d, J = 11.6 Hz, 1 H), 4.06 (dd, J = 10.0, 3.6 Hz, 1 H), 3.95 (dd, J = 10.0, 2.8 Hz, 1 H), 3.88 (br d, J = 2.8 Hz, 1 H), 3.73 (br s, 1 H), 3.72 (dd, J = 14.4, 6.5 Hz, 1 H), 3.49 (dd, J = 14.4, 8.0 Hz, 1 H), 3.37 (s, 3 H), 1.68 (br s, 1 H); 13 C NMR (75 MHz, CDCl 3 ): δ 138.7 (C), 138.4 (C), 138.2 (C), 128.6 (2 C, CH), 128.5 (2 C, CH), 128.43 (2 C, CH), 128.35 (2 C, CH), 128.1 (2 C, CH), 128.0 (CH), 127.7 (CH), 127.60 (CH), 127.55 (2 C, CH), 98.8 (CH), 79.1 (CH), 76.5 (CH), 75.1 (CH), S4
74.4 (CH 2 ), 73.62 (CH 2 ), 73.59 (CH 2 ), 70.2 (CH), 62.4 (CH 2 ), 55.4 (CH 3 ); MS (ESI + ) m/z (%) 482.3 (100, [M+NH 4 ] + ), 487.2 (40, [M+Na] + ), 951.4 (30, [2M+Na] + ); ESIHRMS calcd for C 28 H 36 NO 6 (M+NH 4 ) 482.2543, found 482.2552. Methyl 2,3,4-tri-O-benzyl-6-acetylthio- -D-galactopyranoside (2). To a solution of 1 (1.75 g, 3.77 mmol) in anhydrous THF (68.5 ml), were added, at 0 C, PPh 3 (1.98 g, 7.53 mmol), followed by DEAD (40% in hexane; 3.5 ml, 7.5 mmol) dropwise and the reaction mixture was stirred at this temperature for 30 min. Then, AcSH (0.54 ml, 7.5 mmol) was added and the reaction mixture was allowed to warm up to room temperature and stirred overnight. The reaction mixture was diluted with a saturated solution of NaHCO 3, the organic product was extracted with CH 2 Cl 2, which was dried over Na 2 SO 4 and concentrated under vacuum. After purification on a silica cartridge (70:30 Heptane/AcOEt), the desired product was obtained as a colorless oil (1.79 g, 91%). [α] 20 D = 11.04 (c 0.48, CHCl 3 ); IR υ max (cm -1 ): 2906, 1690; 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.48 (m, 15 H), 5.05 (d, J = 11.4 Hz, 1 H), 4.91 (d, J = 11.9 Hz, 1 H), 4.86 (d, J = 12.3 Hz, 1 H), 4.79 (d, J = 11.9 Hz, 1 H), 4.71 (d, J = 12.3 Hz, 1 H), 4.68 (d, J = 4.5 Hz, 1 H), 4.66 (d, J = 11.4 Hz, 1 H), 4.06 (dd, J = 9.9, 4.5 Hz, 1 H), 3.96 (dd, J = 9.9, 2.7 Hz, 1 H), 3.92 (dd, J = 2.7, 1.0 Hz, 1 H), 3.71 (ddd, J = 7.9, 5.9, 1.0 Hz, 1 H), 3.40 (s, 3 H), 3.09 (dd, J = 13.5, 7.9 Hz, 1 H), 3.00 (dd, J = 13.7, 5.9 Hz, 1 H), 2.33 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 195.3 (C), 138.6 (C), 138.2 (2 C), 128.31 (2 CH), 128.27 (2 CH), 128.2 (2 CH), 128.0 (2 CH), 127.7 (2 CH), 127.6 (2 CH), 127.5 (CH), 127.4 (2 C, CH), 98.6 (CH), 79.1 (CH), 76.6 (CH), 76.1 (CH), 76.0 (CH), 74.7 (CH 2 ), 73.44 (CH 2 ), 73.37 (CH 2 ), 69.5 (CH), 55.1 (CH 3 ), 30.4 (CH 3 ), 29.9 (CH 2 ); MS (ESI + ) m/z (%) 540.6 (100, [M+NH 4 ] + ), 545.6 (40, [M+Na] + ); ESIHRMS calcd for C 30 H 38 NO 6 S (M+NH 4 ) 540.2420, found 540.2414. Methyl 2,3,4-tri-O-benzyl-6-thio- -D-galactopyranoside (3). To a solution of 2 (41 mg, 0.078 mmol) in anhydrous DMF (0.9 ml), was added hydrazine monohydrate (7 μl, 0.14 mmol) and the reaction mixture was stirred at room temperature for 10 min. Then acetic acid (8 μl, 0.14 mmol) was added and the reaction mixture was stirred at room temperature for 1 h. The reaction mixture was diluted with water and extracted with MTBE, which was dried over Na 2 SO 4 and concentrated under vacuum. After purification on a silica cartridge (80:20 Heptane/AcOEt), the desired product was obtained as a colorless oil (31.1 mg, 83%); [α] 20 D = 14.52 (c 2.21, CHCl 3 ); IR υ max (cm -1 ): 2945, 2559; 1 H NMR (300 MHz, CDCl 3 ): δ 7.23-7.46 (m, 15 H), 5.00 (d, J = 11.6 Hz, 1 H), 4.91 (d, J = 11.6 Hz, 1 H), S5
4.85 (d, J = 12.2 Hz, 1 H), 4.78 (d, J = 11.6 Hz, 1 H), 4.69 (d, J = 12.2 Hz, 1 H), 4.67 (d, J = 3.9 Hz, 1 H), 4.66 (d, J = 11.6 Hz, 1 H), 4.05 (dd, J = 3.7, 1.0 Hz, 1 H), 3.92-3.98 (m, 2 H), 3.65 (t, J = 6.8 Hz, 1 H), 3.40 (s, 3 H), 2.73 (ddd, J = 13.6, 7.4, 7.2 Hz, 1 H), 2.40 (ddd, J = 13.6, 10.3, 6.6 Hz, 1 H), 1.26 (dd, J = 10.2, 7.2 Hz, 1 H); 13 C NMR (75 MHz, CDCl 3 ): δ 138.7 (C), 138.4 (C), 138.3 (C), 128.6 (2 CH), 128.43 (2 CH), 128.35 (2 CH), 128.1 (2 CH), 127.9 (2 CH), 127.7 (2 CH), 127.6 (CH), 127.5 (2 CH), 98.8 (CH), 79.4 (CH), 76.4 (CH), 74.8 (CH), 74.5 (CH 2 ), 73.61 (CH 2 ), 73.58 (CH 2 ), 72.3 (CH), 55.5 (CH 3 ), 24.9 (CH 2 ); MS (ESI + ) m/z (%) 498.2 (100, [M+NH 4 ] + ), 503.2 (80, [M+Na] + ); ESIHRMS calcd for C 28 H 36 NO 5 S (M+NH 4 ) 498.2314, found 498.2307. Methyl 4,6-O-benzylidene-2-O-benzoyl-β-D-guloopyranoside (5). 1 To a solution of compound 4 2 (607.8 mg, 1.57 mmol) in CH 2 Cl 2 (12.1 ml) was added dry pyridine (0.98 ml, 12.1 mmol). The reaction mixture was cooled to 0 C and triflic anhydride (0.53 ml, 3.15 mmol) was added dropwise. The reaction mixture was allowed to warm up to room temperature and stirred for further 6 h. The reaction mixture was washed with saturated NaHCO 3 solution, dried over Na 2 SO 4 and the solvent was removed under vacuum. The triflate intermediate was obtained after purification on a silica gel cartridge (CH 2 Cl 2 ) as a white foam (774.7 mg, 95%). To a solution of this product (774 mg, 1.49 mmol) in CH 3 CN (10.5 ml) was added TBANO 2 (1.23 g, 4.25 mmol). The reaction mixture was stirred at room temperature overnight and the solvent was removed. Water was added and the organic product was extracted with AcOEt which was dried over Na 2 SO 4 and and concentrated under vacuum. The desired product was obtained after purification on a silica gel cartridge (95:5 CH 2 Cl 2 /AcOEt) as a yellow foam (387.1 mg, 63%). [α] 20 D = -1.2 (c 1, CHCl 3 ); IR υ max (cm - 1 ): 3505, 1731; 1 H NMR (300 MHz, CDCl 3 ): δ 8.03-8.09 (m, 2 H), 7.33-7.63 (m, 8 H), 5.58 (s, 1 H), 5.37 (dd, J = 8.4, 3.2 Hz, 1 H), 4.98 (d, J = 8.4 Hz, 1 H), 4.36-4.42 (m, 2 H), 4.12-4.14 (m, 1 H), 4.11 (dd, J = 12.4, 1.9 Hz, 1 H), 3.89-3.92 (m, 1 H), 3.57 (s, 3 H), 2.33 (br s, 1 H); 13 C NMR (75 MHz, CDCl 3 ): δ 165.1 (C), 137.6 (C), 133.4 (C), 129.8 (2 CH), 129.1 (2 CH), 128.5 (2 CH), 128.2 (2 CH), 126.4 (2 CH), 101.3 (CH), 98.9 (CH), 76.2 (CH), 71.1 (CH), 69.4 (CH), 69.3 (CH 2 ), 65.7 (CH), 56.5 (CH 3 ); MS (ESI + ) m/z (%) 404.2 (30, [M+NH 4 ] + ); ESIHRMS calcd for C 21 H 26 NO 7 (M+NH 4 ) 404.1709, found 404.1691. Methyl 4,6-O-benzylidene-2-O-benzoyl-3-thioacetyl-β-D-galactopyranoside (6). S6
To a solution of 5 (510 mg, 1.32 mmol) in CH 2 Cl 2 (10.2 ml) was added dry pyridine (0.82 ml, 10.2 mmol). The reaction mixture was cooled to 0 C and triflic anhydride (0.44 ml, 2.64 mmol) was added dropwise. The reaction mixture was allowed to warm up to room temperature and stirred for further 6 h. The reaction mixture was washed with saturated NaHCO 3 solution, dried over Na 2 SO 4 and the solvent was removed under vacuum. The triflate intermediate was obtained after purification on a silica gel cartridge (CH 2 Cl 2 ) as a yellow syrup (643 mg, 94%). To a solution of this intermediate (643 mg, 1.24 mmol) in DMF (4.1 ml) was added KSAc (425.2 mg, 3.72 mmol). The reaction mixture was stirred at 60 C for 5 h. Water was added and the organic product was extracted with MTBE which was dried over Na 2 SO 4, filtered and the solvent was removed under vacuum. The desired product was obtained, after purification on a silica gel cartridge (80:20 Heptane/AcOEt), as a yellowish foam (380.6 mg, 69%). [α] 20 D = 97.5 (c 1.89, CHCl 3 ); IR υ max (cm -1 ): 2866, 1727, 1697; 1 H NMR (300 MHz, CDCl 3 ): δ 7.94-8.08 (m, 2 H), 7.32-7.63 (m, 8 H), 5.56 (s, 1 H), 5.45 (dd, J = 11.5, 7.9 Hz, 1 H), 4.65 (d, J = 7.9 Hz, 1 H), 4.39 (dd, J = 12.5, 1.4 Hz, 1 H), 4.25 (dd, J = 11.5, 3.4 Hz, 1 H), 4.14 (dd, J = 3.4, 0.8 Hz, 1 H), 4.10 (dd, J = 12.5, 1.8 Hz, 1 H), 3.70-3.73 (m, 1 H), 3.51 (s, 3 H), 2.20 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 194.9 (C), 165.3 (C), 137.4 (C), 133.1 (C), 129.9 (2 CH), 129.0 (2 CH), 128.3 (2 CH), 128.2 (2 CH), 126.2 (2 CH), 103.2 (CH), 101.3 (CH), 75.9 (CH), 68.99 (CH 2 ), 68.95 (CH), 68.5 (CH), 56.4 (CH 3 ), 46.9 (CH), 30.5 (CH 3 ); MS (ESI + ) m/z (%) 462.2 (100, [M+NH 4 ] + ); ESIHRMS calcd for C 23 H 28 NO 7 S (M+NH 4 ) 462.1586, found 462.1590. Methyl 4,6-O-benzylidene-2-O-benzoyl-3-thio-β-D-galactopyranoside (7). To a solution of 6 (200 mg, 0.45 mmol) in DMF (3.8 ml) was added hydrazine acetate (62.2 mg, 0.67 mmol). The reaction mixture was stirred at room temperature for 2 h. Water was added and the organic product was extracted with MTBE which was dried over Na 2 SO 4, filtered and the solvent was removed under vacuum. The desired product was obtained, after purification on a silica gel cartridge (70:30 Heptane/AcOEt), as a yellowish foam (173.9 mg, 96%). [α] 20 D = 79.9 (c 1.11, CHCl 3 ); IR υ max (cm -1 ): 2923, 2500, 1723; 1 H NMR (300 MHz, CDCl 3 ): δ 8.03-8.11 (m, 2 H), 7.35-7.60 (m, 8 H), 5.60 (s, 1 H), 5.33 (dd, J = 11.2, 7.9 Hz, 1 H), 4.53 (d, J = 7.9 Hz, 1 H), 4.38 (dd, J = 12.5, 1.4 Hz, 1 H), 4.16 (dd, J = 3.2, 0.9 Hz, 1 H), 4.11 (dd, J = 12.5, 1.9 Hz, 1 H), 3.61-3.64 (m, 1 H), 3.51 (s, 3 H), 3.14 (td, J = 11.0, 3.2 Hz, 1 H), 2.22 (d, J = 10.8 Hz, 1 H); 13 C NMR (75 MHz, CDCl 3 ): δ 165.5 (C), 137.4 (2 C), 133.1 (CH), 129.9 (2 CH), 129.1 (CH), 128.34 ( CH), 128.28 (CH), 128.2 (2 CH), 126.3 (2 CH), 103.1 (CH), 101.5 (CH), 76.6 (CH), 72.4 (CH), 69.01 (CH 2 ), 68.95 (CH), 56.3 (CH 3 ), 43.8 (CH); MS (ESI + ) m/z (%) 420.1 (100, [M+NH 4 ] + ); ESIHRMS calcd for C 21 H 26 NO 6 S (M+NH 4 ) 420.1481, found 420.1476. Methyl 2,3,6-tri-O-benzyl-4-acetylthio- -D-galactopyranoside (9). S7
To a solution of 8 3 (221 mg, 0.48 mmol) in anhydrous THF (2.8 ml), was added 1 M NaHMDS in THF (0.57 ml, 0.57 mmol) at -78 C and the reaction mixture was stirred at this temperature for 30 min. Comin s reagent (224.2 mg, 0.57 mmol) was added and the reaction mixture was stirred at -78 C for 1 h 30. Water was added and the organic product was extracted with CH 2 Cl 2 which was dried over Na 2 SO 4 and concentrated under vacuum. To a solution of the crude material in DMF (2.4 ml) was added AcSK (108.7 mg, 0.95 mmol) and the reaction was stirred at room temperature overnight. Water was added and the organic product was extracted with CH 2 Cl 2 which was dried over Na 2 SO 4 and concentrated under vacuum. The desired product was obtained after purification on a silica cartridge (80:20 Heptane/AcOEt) as a colorless oil (149.9 mg, 60%); [α] 20 D = 29.58 (c 0.91, CHCl 3 ); IR υ max (cm -1 ): 2908, 1694; 1 H NMR (300 MHz, CDCl 3 ): δ 7.23-7.41 (m, 15 H), 4.86 (d, J = 12.0 Hz, 1 H), 4.68 (d, J = 11.2 Hz, 1H), 4.63 (J = 12.0 Hz, 1 H), 4.63 (d, J = 3.7 Hz, 1 H), 4.56 (d, J = 11.2 Hz, 1 H), 4.54 (d, J = 12.0 Hz, 1 H), 4.47 (dd, J = 4.5, 1.6 Hz, 1 H), 4.46 (d, J = 12.0 Hz, 1 H), 4.30 (ddd, J = 6.7, 5.1, 1.6 Hz, 1 H), 4.17 (dd, J = 10.0, 4.5 Hz, 1 H), 3.59 (dd, J = 10.0, 6.7 Hz, 1 H), 3.52 (dd, J = 10.0, 5.2 Hz, 1 H), 3.46 (dd, J = 10.0, 3.7 Hz, 1 H), 3.39 (s, 3 H), 2.37 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 194.4 (C), 138.5 (C), 138.1 (C), 138.0 (C), 128.40 (2 CH), 128.37 (2 CH), 128.3 (2 CH), 128.0 (2 CH), 127.9 (2 CH), 127.74 (CH), 127.69 (CH), 127.7 (CH), 127.64 (CH), 127.60 (CH), 98.9 (CH), 77.6 (CH), 76.4 (CH), 73.8 (CH 2 ), 73.5 (CH 2 ), 72.1 (CH 2 ), 70.6 (CH 2 ), 68.1 (CH), 55.4 (CH 3 ), 47.4 (CH), 31.0 (CH 3 ); MS (ESI + ) m/z (%) 540.2 (60, [M+NH 4 ] + ), 545.2 (100, [M+Na] + ), 1067.4 (30, [2M+Na] + ); ESIHRMS calcd for C 30 H 34 NaO 6 S (M+Na) 545.1974, found 545.1960. Methyl 2,3,6-tri-O-benzyl-4-thio- -D-galactopyranoside (10). To a solution of 9 (48.5 mg, 0.093 mmol) in anhydrous DMF (1 ml), was added hydrazine monohydrate (8 μl, 0.16 mmol) and the reaction mixture was stirred at room temperature for 10 min. Then acetic acid (9 μl, 0.16 mmol) was added and the reaction mixture was stirred at room temperature for 1 h. To the reaction mixture was added water and the organic product was extracted with MTBE which was dried over Na 2 SO 4 and concentrated under vacuum. After purification on a silica cartridge (80:20 Heptane/AcOEt), the desired product was obtained as a colorless oil (42.5 mg, 95%); [α] 20 D = 44.02 (c 0.92, CHCl 3 ); IR υ max (cm -1 ): 2906, 2505; 1 H NMR (300 MHz, CDCl 3 ): δ 7.14-7.36 (m, 15 H), 4.78 (d, J = 11.9 Hz, 1 H), 4.62 (br s, 2 H), 4.59 (J = 11.9 Hz, 1 H), 4.57 (d, J = 3.1 Hz, 1 H), 4.52 (d, J = 11.8 Hz, 1 H), 4.46 (d, J = 11.8 Hz, 1 H), 4.12 (td, J = 6.1, 1.9 Hz, 1 H), 3.95 (dd, J = 9.9, 4.4 Hz, 1 H), 3.85 (dd, J = 9.9, 3.1 Hz, 1 H), 3.51-3.57 (m, 1 H), 3.55 (d, J = 6.3 Hz, 2 H), 3.31 (s, 3 H), 1.60 (d, J = 5.7 Hz, 1 H); 13 C NMR (75 MHz, CDCl 3 ): δ 138.4 (C), 138.2 (C), 137.9 (C), 128.4 (3 S8
CH), 128.3 (3 CH), 128.0 (3 CH), 127.7 (3 CH), 127.6 (3 CH), 98.9 (CH), 76.8 (CH), 75.5 (CH), 73.7 (CH 2 ), 73.6 (CH 2 ), 71.9 (CH 2 ), 70.4 (CH 2 ), 67.6 (CH), 55.2 (CH 3 ), 42.9 (CH); MS (ESI + ) m/z (%) 498.2 (60, [M+NH 4 ] + ), 503.2 (100, [M+Na] + ), 983.4 (20, [2M+Na] + ); ESIHRMS calcd for C 28 H 32 NaO 5 S (M+Na) 503.1868, found 503.1871. General procedure for S-glycosylation with a sialyl phosphate donor: A solution of sialyl phosphate donor 11α,β, 4 acceptor (2 equiv. or 1.2 equiv.) with pulverized 4 Å MS (2 g.mmol -1 ) in dry CH 2 Cl 2 (0.04 M) or CH 2 Cl 2 /CH 3 CN (2:1) (0.04 M) was stirred under argon at room temperature for 2 h. The reaction mixture was then cooled to -78 C followed by addition of TMSOTf (1 equiv.). After being stirred at the same temperature for 1.25 h the reaction mixture was quenched with triethylamine (2 equiv), diluted with CH 2 Cl 2 and filtered through a pad of Celite. The filtrate was washed with brine, dried over Na 2 SO 4, filtered and concentrated under vacuum. Methyl (5-acetamido-2-benzylthio-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-Dglycero- -D-galacto-non-2-ulopyranoside)onate (12). This compound was prepared according to the general procedure for S-glycosylation with a sialyl phosphate donor from sialyl α-phosphate 11α (40 mg, 0.06 mmol) and benzyl mercaptan (14 µl, 0.12 mmol) in CH 2 Cl 2 (0.65 ml). Purification on a silica cartridge by HPLC (70:30 Heptane/AcOEt) gave the desired products as a colorless oil (12.1 mg, 80%, 83% brsm ); [α] 20 D = 66.52 (c 0.46, CHCl 3 ); IR υ max (cm -1 ): 2955, 1796, 1738; 1 H NMR (300 MHz, CDCl 3 ): δ 7.18-7.35 (m, 5 H), 5.61 (dd, J = 7.0, 1.5 Hz, 1 H), 5.52 (ddd, J = 7.0, 6.7, 2.6 Hz, 1 H), 4.39-4.45 (m, 1 H), 4.42 (dd, J = 9.4, 1.5 Hz, 1 H), 4.14 (dd, J = 12.4, 6.7 Hz, 1 H), 3.97 (d, J = 13.7 Hz, 1 H), 3.91 (ddd, J = 12.0, 11.0, 3.5 Hz, 1 H), 3.85 (d, J = 13.7 Hz, 1 H), 3.72 (dd, J = 11.0, 9.4 Hz, 1 H), 3.52 (s, 3 H), 3.03 (dd, J = 12.0, 3.5 Hz, 1 H), 2.48 (s, 3 H), 2.18 (s, 3 H), 2.17 (s, 3 H), 2.11 (t, J = 12.4 Hz, 1 H), 2.02 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 171.8 (C), 170.7 (C), 170.5 (C), 170.1 (C), 168.1 (C, 3 J C-H3ax. = 7.0 Hz), 153.4 (C), 136.3 (C), 129.1 (2 CH), 128.4 (2 CH), 127.3 (CH), 83.6 (C), 76.8 (CH), 75.8 (CH), 72.3 (CH), 69.8 (CH), 62.9 (CH 2 ), 59.3 (CH), 53.0 (CH 3 ), 36.5 (CH 2 ), 33.2 (CH 2 ), 24.7 (CH 3 ), 21.3 (CH 3 ), 21.0 (CH 3 ), 20.8 (CH 3 ); MS (ESI + ) m/z (%) 599.2 (100, [M+NH 4 ] + ); ESIHRMS calcd for C 26 H 35 N 2 O 12 S (M+ NH 4 ) 599.1911, found 599.1895. Methyl (5-acetamido-2-benzylthio-7,8,9-tri-O-acetyl-3,5-dideoxy-D-glycero-β-D-galactonon-2-ulopyranoside)onate (13). S9
This compound was prepared according to the general procedure for S-glycosylation with a sialyl phosphate donor from sialyl α-phosphate 11α (39 mg, 0.058 mmol) and benzyl mercaptan (5 equiv., 34.3 µl, 0.29 mmol) in CH 2 Cl 2 (0.65 ml). Purification on a silica cartridge by HPLC (70:30 Heptane/AcOEt) gave 13 as a colorless oil (25.3 mg, 78%); [α] 20 D = 34.48 (c 0.87, CHCl 3 ); IR υ max (cm -1 ): 3362, 2956, 1743, 1658; 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.37 (m, 5 H), 5.31 (dd, J = 6.1, 2.2 Hz, 1 H), 5.20 (ddd, J = 7.0, 6.1, 2.4 Hz, 1 H), 5.11 (br d, J = 10.0 Hz, 1 H), 4.43 (dd, J = 12.4, 2.4 Hz, 1 H), 4.09-4.17 (m, 2 H), 4.00 (dd, J = 12.4, 7.0 Hz, 1 H), 3.82-3.93 (m, 1 H), 3.85 (s, 3 H), 3.78 (d, J = 12.6 Hz, 1 H), 3.69 (d, J = 12.6 Hz, 1 H), 3.04 (td, J = 12.0, 4.7 Hz, 1 H), 2.33 (t, J = 13.4 Hz, 1 H), 2.23 (dd, J = 13.4, 4.7 Hz, 1 H), 2.13 (s, 3 H), 2.07 (s, 3 H), 2.04 (s, 3 H), 1.92 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 170.7 (C), 170.43 (C), 170.37 (C), 170.3 (C), 169.6 (C, 3 J C-H3ax. 0 Hz), 138.0 (C), 119.0 (2 CH), 128.6 (2 CH), 127.2 (CH), 94.3 (C), 71.7 (CH), 70.8 (CH), 68.5 (CH), 62.7 (CH 2 ), 53.5 (CH 3 ), 48.6 (CH), 42.7 (CH), 38.3 (CH 2 ), 34.1 (CH 2 ), 23.3 (CH 3 ), 21.0, 20.9, 20.8 (3 CH 3 ); MS (ESI + ) m/z (%) 556.2 (100, [M+H] + ), 1133.4 (30, [2M+Na] + ); ESIHRMS calcd for C 25 H 34 NO 11 S (M+H) 556.1853, found 556.1861. Methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-2-(4- methoxyphenyl)thio-d-glycero- -D-galacto-non-2-ulopyranoside)onate (14). This compound was prepared according to the general procedure for S-glycosylation with a sialyl phosphate donor from sialyl α-phosphate 11α (49.2 mg, 0.074 mmol) and 4- methoxybenzenethiol (18 µl, 0.15 mmol) in CH 2 Cl 2 (1.85 ml). Purification on a silica cartridge by HPLC (60:40 Heptane/AcOEt) gave the desired product as a white foam (32.2 mg, 73%); [α] 20 D = 6.7 (c 2.25, CHCl 3 ); IR υ max (cm -1 ): 2955, 1796, 1738; 1 H NMR (300 MHz, CDCl 3 ): δ 7.42-7.48 (m, 2 H), 6.83-6.89 (m, 2 H), 5.52 (dd, J = 6.0, 1.5 Hz, 1 H), 5.32 (ddd, J = 6.8, 6.0, 2.9 Hz, 1 H), 4.41 (dd, J = 12.2, 2.9, 1 H), 4.31 (dd, J = 9.5, 1.5 Hz, 1 H), 4.19 (dd, J = 12.2, 6.8 Hz, 1 H), 3.94 (ddd, J = 12.6, 11.2, 3.6 Hz, 1 H), 3.82 (s, 3 H), 3.62 (s, 3 H), 3.58 (dd, J = 11.2, 9.4 Hz, 1 H), 3.08 (dd, J = 12.1, 3.6 Hz, 1 H), 2.45 (s, 3 H), 2.16 (s, 3 H), 2.068 (s, 3 H), 2.065 (s, 3 H), 2.08 (dd, J = 12.6, 12.1 Hz, 1 H); 13 C NMR (75 MHz, CDCl 3 ): δ 171.9 (C), 170.7 (C), 170.2 (C), 170.0 (C), 168.2 (C, 3 J C-H3ax. = 7.6 Hz), 161.4 (C), 153.4 (C), 138.4 (2 CH), 118.7 (C), 114.5 (2 CH), 87.7 (C), 77.3 (CH), 75.8 (CH), 72.6 (CH), 70.6 (CH), 62.6 (CH 2 ), 59.1 (CH), 55.4 (CH 3 ), 53.1 (CH 3 ), 36.5 (CH 2 ), 24.7 (CH 3 ), 21.1 (CH 3 ), 20.9 (CH 3 ), 20.8 (CH 3 ); MS (ESI + ) m/z (%) 615.2 (100, [M+NH 4 ] + ), 620.1 (90, [M+Na] + ), 1217.3 (30, [2M+Na] + ); ESIHRMS calcd for C 26 H 35 N 2 O 13 S (M+ NH 4 ) 615.1860, found 615.1860. Methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-2-tert-butylthio-Dglycero- -D-galacto-non-2-ulopyranoside)onate (15). S10
This compound was prepared according to the general procedure for S-glycosylation with a sialyl phosphate donor from sialyl α-phosphate 11α (47.9 mg, 0.072 mmol) and tert-butyl mercaptan (16 µl, 0.14 mmol) in CH 2 Cl 2 (1.8 ml). Purification on a silica cartridge by HPLC (60:40 Heptane/AcOEt) gave the desired products as a white foam (35.1 mg, 89%); [α] 20 D = 27.1 (c 0.55, CHCl 3 ); IR υ max (cm -1 ): 1796, 1737; 1 H NMR (300 MHz, CDCl 3 ): δ 5.58 (dd, J = 7.6, 1.3 Hz, 1 H), 5.43 (ddd, J = 7.6, 6.4, 2.6 Hz, 1 H), 4.51 (dd, J = 9.5, 1.3 Hz, 1 H), 4.37 (dd, J = 12.3, 2.6 Hz, 1 H), 4.11 (dd, J = 12.3, 6.4 Hz, 1 H), 3.86 (ddd, J = 12.7, 11.3, 3.5 Hz, 1 H), 3.81 (s, 3 H), 3.68 (dd, J = 11.3, 9.5 Hz, 1 H), 3.01 (dd, J = 12.0, 3.5 Hz, 1 H), 2.48 (s, 3 H), 2.16 (s, 3 H), 2.14 (s, 3 H), 2.03 (s, 3 H), 2.10-2.19 (m, 1 H), 1.37 (s, 9 H); 13 C NMR (75 MHz, CDCl 3 ): δ 171.9 (C), 170.7 (2 C), 170.3 (C), 169.7 (C, 3 J C-H3ax. = 5.8 Hz), 153.4 (C), 85.3 (C), 76.6 (C), 75.5 (CH), 72.1 (CH), 70.1 (CH), 62.6 (CH 2 ), 59.5 (CH), 53.1 (CH 3 ), 48.5 (C), 38.5 (CH 2 ), 31.6 (3 CH 3 ), 24.8 (CH 3 ), 21.1 (CH 3 ), 20.9 (CH 3 ), 20.7 (CH 3 ); MS (ESI + ) m/z (%) 565.2 (100, [M+NH 4 ] + ), 570.2 (30, [M+Na] + ); ESIHRMS calcd for C 23 H 37 N 2 O 12 S (M+NH 4 ) 565.2067, found 565.2055. Methyl (2-S-(methyl 2,3,4-tri-O-benzyl-6-thio- -D-galactopyranoside)-5-N-acetyl-7,8,9- tri-o-acetyl-5-n,4-o-carbonyl-3,5-dideoxy-d-glycero- -D-galacto-non-2- ulopyranoside)onate (16). This compound was prepared according to the general procedure for S-glycosylation with a sialyl phosphate donor from sialyl α-phosphate 11α (50 mg, 0.075 mmol) and 3 (43.2 mg, 0.090 mmol) in CH 2 Cl 2 (1.9 ml). Purification on a silica gel cartridge (70:30 Heptane/AcOEt) gave the desired product as colorless oil (39.2 mg, 56%, 70% brsm); [α] 20 D = 55.24 (c 1.0, CHCl 3 ); IR υ max (cm -1 ): 2929, 1797, 1740; 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.43 (m, 15 H), 5.64 (dd, J = 8.7, 1.1 Hz, 1 H), 5.41 (ddd, J = 8.5, 5.7, 2.8 Hz, 1 H), 5.02 (d, J = 10.9 Hz, 1 H), 4.840 (d, J = 11.9 Hz, 1 H), 4.841 (d, J = 12.4 Hz, 1 H), 4.79 (d, J = 12.4 Hz, 1 H), 4.75 (d, J = 10.9 Hz, 1 H), 4.67 (d, J = 11.9 Hz, 1 H), 4.62 (d, J = 3.7 Hz, 1 H), 4.33 (dd, J = 12.9, 2.8 Hz, 1 H), 4.29 (dd, J = 9.5, 1.1 Hz, 1 H), 4.05 (dd, J = 12.9, 5.7 Hz, 1H), 3.95-4.01 (m, 2 H), 3.89 (ddd, J = 14.8, 11.0, 3.5 Hz, 1 H), 3.85 (dd, J = 10.2, 2.8 Hz, 1 H), 3.74 (s, 3 H), 3.65 (dd, J = 11.0, 9.5 Hz, 1 H), 3.50 (dd, J = 9.1, 3.9 Hz, 1 H), 3.38 (s, 3 H), 2.91-3.10 (m, 3 H), 2.49 (s, 3 H), 2.14 (s, 3 H), 2.13 (s, 3 H), 2.05 (dd, J = 10.8, 3.5 Hz, 1 H), 1.96 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 171.6 (C), 170.7 (C), 170.04 (C), 169.98 (C), 168.7 (C, 3 J C-H3ax. = 5.7 Hz), 153.3 (C), 139.0 (C), 138.8 (C), 138.4 (C), 128.4 (3 CH), 128.2 (3 CH), 128.0 (3 CH), 127.7 (2 CH), 127.5 (2 CH), 127.4 (2 CH), 98.9 (CH), 82.7 (C), 79.0 (CH), 77.2 (CH), S11
76.1, 75.98, 75.92 (3 CH), 74.9 (CH 2 ), 73.6 (CH 2 ), 72.9 (CH 2 ), 71.5 (CH), 69.8 (CH), 68.6 (CH), 62.7 (CH 2 ), 59.3 (CH), 55.4 (CH 3 ), 53.1 (CH 3 ), 36.4 (CH 2 ), 30.0 (CH 2 ), 24.7 (CH 3 ), 21.4 (CH 3 ), 21.0 (CH 3 ), 20.7 (CH 3 ); MS (ESI + ) m/z (%) 955.3 (80, [M+NH 4 ] + ), 960.3 (100, [M+Na] + ); ESIHRMS calcd for C 47 H 55 NNaO 17 S (M+Na) 960.3088, found 960.3087. Methyl (2-S-(methyl 4,6-O-benzylidene-2-O-benzoyl-3-thio-β-D-galactopyranoside)-5-N- acetyl-7,8,9-tri-o-acetyl-5-n,4-o-carbonyl-3,5-dideoxy-d-glycero- -D-galacto-non-2- ulopyranoside)onate (17). This compound was prepared according to the general procedure for S-glycosylation with a sialyl phosphate donor from sialyl α-phosphate 11α (52.3 mg, 0.078 mmol) and 7 (37.8 mg, 0.094 mmol) in CH 2 Cl 2 /CH 3 CN (2:1) (1.8 ml). Purification on a silica gel cartridge (60:40 Heptane/AcOEt) gave the desired product as a white foam (57.7 mg, 86%); [α] 20 D = 46.15 (c 0.13, CHCl 3 ); IR υ max (cm -1 ): 1736; 1 H NMR (300 MHz, CDCl 3 ): δ 8.14-8.19 (m, 2 H), 7.33-7.61 (m, 8 H), 5.65 (ddd, J = 9.9, 6.7, 2.4 Hz, 1 H), 5.54 (dd, J = 9.9, 1.4 Hz, 1 H), 5.46 (s, 1 H), 5.23 (dd, J = 11.8, 7.6 Hz, 1 H), 4.90 (d, J = 7.6 Hz, 1 H), 4.51 (dd, J = 12.3, 2.4 Hz, 1 H), 4.36 (dd, J = 12.3, 1.2 Hz, 1 H), 4.28 (dd, J = 9.4, 1.4 Hz, 1 H), 4.11 (dd, J = 12.3, 6.7 Hz, 1 H), 4.06 (dd, J = 12.3, 2.4 Hz, 1 H), 3.89 (dd, J = 11.8, 3.3 Hz, 1 H), 3.78-3.86 (m, 2 H), 3.77 (s, 3 H), 3.65-3.68 (m, 1 H), 3.47-3.56 (m, 1 H), 3.50 (s, 3 H), 2.93 (dd, J = 12.1, 3.3 Hz, 1 H), 2.45 (s, 3 H), 2.21 (s, 3 H), 2.09 (s, 3 H), 2.03-2.14 (m, 1 H), 1.46 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 171.7 (C), 170.8 (C), 170.4 (C), 170.1 (C), 169.4 (C, 3 J C-H3ax. = 7.2 Hz), 166.0 (C), 153.2 (C), 137.6 (C), 133.1 (C), 130.4 (CH), 130.3 (2 CH), 128.9 (CH), 128.3 (2 CH), 128.1 (2 CH), 126.3 (2 CH), 102.7 (CH), 101.5 (CH), 81.7 (C), 75.85 (CH), 75.81 (CH), 75.79 (CH), 71.2 (CH), 69.2 (CH 2 ), 69.0 (CH), 68.0 (CH), 67.7 (CH), 63.5 (CH 2 ), 58.9 (CH), 56.7 (CH 3 ), 53.1 (CH 3 ), 45.7 (CH), 35.9 (CH 2 ), 24.6 (CH 3 ), 21.6 (CH 3 ), 20.9 (CH 3 ), 20.4 (CH 3 ); MS (ESI + ) m/z (%) 877.3 (100, [M+NH 4 ] + ); ESIHRMS calcd for C 40 H 49 N 2 O 18 S (M+NH 4 ) 877.2701, found 877.2740. Methyl (2-S-(methyl 2,3,6-tri-O-benzyl-4-thio- -D-galactopyranoside)-5-N-acetyl-7,8,9- tri-o-acetyl-5-n,4-o-carbonyl-3,5-dideoxy-d-glycero- -D-galacto-non-2- ulopyranoside)onate (18). S12
This compound was prepared according to the general procedure for S-glycosylation with a sialyl phosphate donor from sialyl α-phosphate 11α (40 mg, 0.060 mmol) and 10 (34.6 ml, 0.072 mmol) in CH 2 Cl 2 (1.5 ml). Purification on a silica gel cartridge (70:30 Heptane/AcOEt) gave the desired product as colorless oil (37.7 mg, 67%, 92% brsm; [α] 20 D = -5.60 (c 1.91, CHCl 3 ); IR υ max (cm -1 ): 2924, 1796, 1744; 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.38 (m, 15 H), 5.54 (dd, J = 8.7, 1.1 Hz, 1 H), 5.37 (ddd, J = 8.7, 5.9, 3.0 Hz, 1 H), 4.98 (d, J = 11.4 Hz, 1 H), 4.77 (d, J = 11.7 Hz, 1 H), 4.76 (d, J = 11.4 Hz, 1 H), 4.58-4.67 (m, 4 H), 4.44 (dd, J = 9.7, 1.1 Hz, 1 H), 4.27-4.34 (m, 2 H), 4.14 (dd, J = 9.7, 4.3 Hz, 1H), 4.01 (dd, J = 12.3, 5.8 Hz, 1 H), 3.65-3.81 (m, 5 H), 3.69 (s, 3 H), 3.39 (s, 3 H), 3.20 (dd, J = 11.0, 9.7 Hz, 1 H), 3.68-3.83 (m, 2 H), 2.48 (s, 3 H), 2.12 (s, 3 H), 1.99 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ 172.0 (C), 170.5, 169.9, 169.5 (3 C), 169.3 (C, 3 J C-H3ax. = 6.6 Hz), 153.4 (C), 138.6 (C), 138.2 (C), 138.1 (C), 128.5 (2 CH), 128.4 (2 CH), 128.3 (2 CH), 128.2 (2 CH), 128.0 (2 CH), 127.9 (2 CH), 127.8 (CH), 127.4 (CH); 127.1 (CH), 98.0 (CH), 82.3 (C), 78.9 (CH), 76.6 (CH), 75.3 (CH 2 ), 74.5 (CH 2 ), 73.3 (CH 2 ), 73.2 (CH 2 ), 71.9 (CH), 71.6 (CH), 70.2 (2 CH), 68.9 (CH), 62.7 (CH 2 ), 58.6 (CH), 55.2 (CH 3 ), 53.2 (CH 3 ), 48.0 (CH), 38.5 (CH 2 ), 24.7 (CH 3 ), 21.1 (CH 3 ), 20.9 (CH 3 ), 20.7 (CH 3 ); MS (ESI + ) m/z (%) 955.4 (40, [M+NH 4 ] + ), 983.4 (100, [M+HCOOH] + ); ESIHRMS calcd for C 47 H 59 N 2 O 17 S (M+NH 4 ) 955.3534, found 955.3560. General procedure for the selective cleavage of the O-acetyl bonds and of the oxazolidinone ring: To a solution of sialoside (1 equiv.) in MeOH (0.05 M) were added few drops of 20 wt% sodium methoxide in MeOH and the mixture was stirred at room temperature for 30 min followed by treatment with Amberlyst 15 ion-exchange resin for 5 min. The mixture was diluted with MeOH and filtered through a sintered funnel containing Celite. The pad was rinsed with MeOH after filtration. The filtrate was concentrated under vacuum and passed through a reverse phase GracePure C18 cartridge (water and then MeOH) to afford the deprotected N-acetamidosialosides without further purification. Methyl (2-S-(methyl 2,3,4-tri-O-benzyl-6-thio- -D-galactopyranoside)-5-N-acetyl-3,5- dideoxy-d-glycero- -D-galacto-non-2-ulopyranoside)onate (19). This compound was prepared according to the general procedure for the selective saponification from 16 (29 mg, 0.031 mmol) and MeONa in MeOH (0.62 ml). The desired product was obtained as a colorless oil (23.7 mg, 98%); [α] 20 D = 45.9 (c 2.15, CH 3 OH); IR υ max (cm -1 ): 3651-3158, 2921, 1716; 1 H NMR (300 MHz, CD 3 OD): δ 7.28-7.50 (m, 15 H), 4.96 (d, J = 11.0 Hz, 1 H), 4.85 (d, J = 11.7 Hz, 1 H), 4.79 (d, J = 11.7 Hz, 1 H), 4.78 (d, J = 11.5 Hz, 1 H), 4.71 (d, J = 3.6 Hz, 1 H), 4.69 (d, J = 11.7 Hz, 1 H), 4.63 (d, J = 11.0 Hz, 1 H), 4.24 (br s, 1 H), 3.94-3.98 (m, 2 H), 3.80-3.91 (m, 3 H), 3.84 (s, 3 H), 3.61-3.75 (m, 3 H), 3.54-3.68 (m, 1 H), 3.48 (dd, J = 10.3, 1.4 Hz, 1 H), 3.41 (s, 3 H), 2.73-2.92 (m, 3 H), 2.04 (s, S13
3 H), 1.84 (dd, J = 12.7, 11.5 Hz, 1 H); 13 C NMR (75 MHz, CD 3 OD): δ 175.2 (C), 172.0 (C, 3 J C-H3ax. = 7.3 Hz), 140.1 (C), 104.0 (C), 139.7 (C), 129.37 (2 CH), 129.36 (2 CH), 128.34 (2 CH), 128.29 (2 CH), 129.2 (2 CH), 128.8 (2 CH), 128.7 (CH), 128.6 (2 CH), 100.0 (CH), 85.1 (C), 80.2, 77.41, 77.36 (3 CH), 76.9 (CH), 76.2 (CH 2 ), 74.3 (CH 2 ), 73.9 (CH 2 ), 72.5 (CH), 71.3 (CH), 69.9 (CH), 68.9 (CH), 64.5 (CH 2 ), 55.9 (CH 3 ), 53.7 (CH), 53.6 (CH 3 ), 42.1 (CH 2 ), 31.3 (CH 2 ), 22.7 (CH 3 ); MS (ESI + ) m/z (%) 803.3 (100, [M+NH 4 ] + ), 808.3 (80, [M+Na] + ); ESIHRMS calcd for C 40 H 55 N 2 O 13 S (M+NH 4 ) 803.3425, found 803.3462. (2-S-(Methyl β-d-galactothiopyranoside)-5-n-acetyl-3,5-dideoxy-d-glycero-α-d-galactonon-2-ulopyranoside)onic acid (20). To a solution of compound 17 (20 mg, 0.023 mmol) in MeOH (0.34 ml) was added NaOH (9.3 mg, 0.23 mmol) in water (0.12 ml). The reaction mixture was stirred at room temperature overnight. Dowex 50W X8, acidic resin was added. After filtration on a sintered funnel, the filtrate was concentrated under vacuum and passed through a reverse phase GracePure C18 cartridge (water then MeOH). The solvent was removed and the product was dissolved in D 2 O for overnight NMR experiments. The solvent was removed under vacuum and the crude product was passed through a reverse phase GracePure C18 cartridge (water). The solvent was removed to give the desired product as a white foam (9 mg, 77%); [α] 20 D = 46.44 (c 0.90, H 2 O); IR υ max (cm -1 ): 3306, 1730; 1 H NMR (300 MHz, D 2 O): δ 4.44 (d, J = 7.1 Hz, 1 H), 5.46 (s, 3 H), 3.73-3.80 (m, 4 H), 3.64-3.70 (m, 3 H), 3.57-3.61 (m, 1 H), 3.60 (s, 3 H), 3.34-3.41 (m, 2 H), 2.84 (dd, J = 12.7, 4.8 Hz, 1 H), 2.05 (s, 3 H), 1.89 (dd, J = 12.7, 11.5 Hz, 1 H); 13 C NMR (75 MHz, D 2 O): δ 175.0 (C), 173.7 (C, 3 J C-H3ax. = 7.5 Hz), 105.0 (CH), 83.2 (C), 77.3 (CH), 75.0 (CH), 71.6 (CH), 68.7 (CH), 68.23 (CH), 68.21 (CH), 68.1 (CH), 62.8 (CH 2 ), 61.1 (CH 2 ), 57.0 (CH 3 ), 51.6 (CH), 50.9 (CH), 40.3 (CH 2 ), 22.1 (CH 3 ); MS (ESI - ) m/z (%) 500.1 (100, [M-H] - ); ESIHRMS calcd for C 18 H 30 NO 13 S (M-H) 500.1438, found 500.1432. Methyl (2-S-(methyl 2,3,6-tri-O-benzyl-4-thio- -D-galactopyranoside)-5-N-acetyl-3,5- dideoxy-d-glycero- -D-galacto-non-2-ulopyranoside)onate (21). This compound was prepared according to the general procedure for the selective cleavage of oxazolidinones from 18 (47.6 mg, 0.051 mmol) and MeONa in MeOH (1 ml). The desired product was obtained as a colorless oil (31.7 mg, 79%); [α] 20 D = 24.6 (c 2.5, CH 3 OH); IR υ max (cm -1 ): 3391, 2929; 1 H NMR (300 MHz, CD 3 OD): δ 7.23-7.53 (m, 15 H), 4.98 (d, J = S14
12.1 Hz, 1 H), 4.72 (d, J = 11.8 Hz, 1 H), 4.68 (d, J = 3.0 Hz, 1H), 4.62 (d, J = 12.1 Hz, 1 H), 4.63 (d, J = 12.4 Hz, 1 H), 4.64 (d, J = 11.8 Hz, 1 H), 4.55 (d, J = 12.4 Hz, 1H), 4.18 (ddd, J = 4.9, 4.9, 2.2 Hz, 1 H), 4.07 (dd, J = 9.6, 4.1 Hz, 1 H), 3.94-3.99 (m, 2 H), 3.87-3.79 (m, 2 H), 3.77 (s, 3 H), 3.72-3.76 (m, 1 H), 3.53-3.70 (m, 6 H), 3.36 (s, 3 H), 2.81 (dd, J = 12.2, 4.7 Hz, 1 H), 2.16 (dd, J = 13.2, 11.3 Hz, 1 H), 2.04 (s, 3 H); 13 C NMR (75 MHz, CD 3 OD): δ 175.3 (C), 172.7 (C, 3 J C-H3ax. = 7.6 Hz), 139.8 (2 C), 139.6 (C), 130.5 (2 CH), 129.6 (2 CH), 129.4 (2 CH), 129.3 (2 CH), 129.2 (2 CH), 128.81 (CH), 128.75 (CH), 128.6 (CH), 128.5 (2 CH), 99.2 (CH), 84.0 (C), 78.8 (CH), 78.0 (CH), 77.5 (CH), 74.3 (2 CH 2 ), 74.2 (CH 2 ), 73.8 (CH 2 ), 72.4 (CH), 71.2 (CH), 70.3 (CH), 70.0 (CH), 64.7 (CH 2 ), 55.7 (CH 3 ), 53.8 (CH 3 ), 53.6 (CH), 47.9 (CH), 30.7 (CH 2 ), 22.6 (CH 3 ); MS (ESI + ) m/z (%) 803.3 (100, [M+NH 4 ] + ), 808.3 (70, [M+Na] + ); ESIHRMS calcd for C 40 H 55 N 2 O 13 S (M+NH 4 ) 803.3425, found 803.3395. (1) Busse, H.; Hakoda, M.; Stanley, M.; Streicher, H. r. J. Carbohydr. Chem. 2007, 26, 159. (2) Dang, N.; Munasinghe, V. R. N.; Overend, W. G. J. Chem. Soc. Perkin Trans. 1 1983, 257. (3) Shie, C. R.; Tzeng, Z. H.; Kulkarni, S. S.; Uang, B. J.; Hsu, C. Y.; Hung, S. C. Angew. Chem. Int. Ed. 2005, 44, 1665. (4) Noel, A.; Delpech, B.; Crich, D. Org. Lett. 2012, 14, 1342. S15
0,9 2,0 1,9 2,0 S16 2,5 2 15,3 7,190 7,205 7,215 7,223 7,238 7,260 7,267 7,287 7,293 7,310 7,316 7,459 7,470 7,487 7,494 7,499 4,749 4,760 4,415 3,279 3,296 3,306 3,311 3,329 3,343 3,386 3,417 3,438 3,449 3,471 3,706 3,730 3,798 3,817 3,837 3,889 8,5 8 7,5 7 1 H NMR (300 MHz, CDCl 3) of compound 22 6,5 6 5,5 5 4,5 4 3,5 3
S17 50 40 30 143,820 126,964 127,764 128,586 99,449 86,767 76,594 77,016 77,438 69,155 69,286 69,875 70,748 63,331 55,085 160 150 140 130 120 13 C NMR (75 MHz, CDCl 3) of compound 22 110 100 90 80 70 60
S18 15,2 7,260 7,277 7,293 7,300 7,306 7,311 7,325 7,335 7,343 7,348 7,354 7,367 7,372 7,394 7,401 7,410 7,429 7,0 2,0 3,371 3,478 3,499 3,684 3,706 3,731 3,879 3,888 3,928 3,937 3,961 3,971 4,042 4,054 4,075 4,087 4,628 4,666 4,683 4,710 4,723 4,740 4,779 4,833 4,873 4,884 4,923 4,963 5,002 1,1 1,677 8 7,5 7 6,5 6 1 H NMR (300 MHz, CDCl 3) of compound 1 5,5 5 4,5 4 3,5 3 2,5 2 1,5
S19 50 45 40 138,162 138,424 138,715 127,553 127,604 127,742 127,982 128,084 128,353 128,433 128,469 128,571 98,831 70,239 73,591 73,620 74,435 75,096 76,478 76,594 77,016 77,445 79,117 62,400 55,354 140 135 130 125 120 115 110 105 13 C NMR (75 MHz, CDCl 3) of compound 1 100 95 90 85 80 75 70 65 60 55
S20 7,455 15,0 7,260 7,288 7,304 7,311 7,316 7,329 7,335 7,343 7,349 7,358 7,365 7,370 7,379 7,384 7,390 7,405 7,412 7,417 7,423 7,426 7,448 7,0 3,1 4,638 4,676 4,692 4,734 4,769 4,808 4,838 4,878 4,892 4,932 5,032 5,070 3,398 3,691 3,711 3,715 3,719 3,909 3,913 3,919 3,922 3,936 3,969 3,978 4,038 4,050 4,071 4,083 2,0 2,991 18 36 53 79 3,125 2,9 2,325 7,5 7 6,5 6 5,5 1 H NMR (300 MHz, CDCl 3) of compound 2 5 4,5 4 3,5 3 2,5 2
S21 195,280 127,364 127,459 127,619 127,655 127,989 128,237 128,273 128,309 138,191 138,613 98,605 69,461 73,373 73,438 74,682 75,991 76,078 76,594 77,016 77,438 79,088 55,129 29,867 30,362 200 190 180 170 160 150 13 C NMR (75 MHz, CDCl 3) of compound 2 140 130 120 110 100 90 80 70 60 50 40 30 20
S22 0,7 2,0 6,0 15,7 1,1 1,228 1,252 1,262 1,286 1,568 2,312 2,351 2,373 2,386 2,397 2,408 2,419 2,431 2,453 2,680 2,704 2,728 2,749 2,773 3,399 3,626 3,649 3,933 3,951 3,960 4,021 4,024 4,032 4,036 4,057 4,060 4,069 4,637 4,661 4,675 4,715 4,760 4,799 4,827 4,867 4,892 4,931 4,985 5,023 7,260 7,273 7,288 7,296 7,301 7,311 7,314 7,322 7,335 7,340 7,349 7,354 7,363 7,368 7,374 7,387 7,396 7,401 7,409 7,415 7,435 7,442 0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 8 1 H NMR (300 MHz, CDCl 3) of compound 3
S23 20 10 138,344 138,431 138,744 127,524 127,582 127,735 127,866 128,099 128,353 128,426 128,586 98,809 72,319 73,584 73,613 74,544 74,769 76,383 76,587 77,016 77,438 79,416 55,456 24,923 140 130 120 110 100 90 13 C NMR (75 MHz, CDCl 3) of compound 3 80 70 60 50 40 30
0,9 2,0 S24 2,0 8,0 7,260 7,365 7,372 7,381 7,389 7,406 7,409 7,433 7,460 7,519 7,526 7,534 7,539 7,552 7,559 7,984 7,989 8,013 5,295 5,416 5,442 5,454 5,480 5,561 3,504 3,714 3,718 4,080 4,086 4,121 4,127 4,140 4,149 4,150 4,228 4,239 4,266 4,277 4,365 4,370 4,407 4,412 4,638 4,665 2,198 8,5 8 7,5 7 6,5 6 1 H NMR (300 MHz, CDCl 3) of compound 6 5,5 5 4,5 4 3,5 3 2,5 2 1,5
S25 20 0 194,932 165,268 126,244 128,163 128,338 129,029 129,887 1380 137,363 101,255 103,161 68,493 68,951 68,987 75,867 76,594 77,016 77,438 56,369 46,908 30,479 200 180 160 140 13 C NMR (75 MHz, CDCl 3) of compound 6 120 100 80 60 40
2,0 S26 2,0 8,0 7,260 7,377 7,383 7,393 7,401 7,415 7,431 7,455 7,460 7,477 7,482 7,541 7,548 7,553 7,558 7,565 7,576 8,057 8,062 8,082 8,086 8,089 5,599 5,302 5,328 5,339 5,365 4,085 4,091 4,126 4,132 4,154 4,157 4,165 4,168 4,359 4,363 4,400 4,405 4,518 4,544 3,502 3,620 3,625 99 3,110 3,136 3,146 3,172 3,183 2,200 2,236 8 7,5 7 6,5 6 1 H NMR (300 MHz, CDCl 3) of compound 7 5,5 5 4,5 4 3,5 3 2,5 2
S27 40 30 20 165,467 137,435 126,288 128,222 128,280 128,346 129,109 129,851 1358 101,477 1092 76,594 77,016 77,438 72,384 68,952 69,010 56,321 43,785 180 170 160 150 140 130 13 C NMR (75 MHz, CDCl 3) of compound 7 120 110 100 90 80 70 60 50
7,1 2,0 S28 16,6 7,358 7,345 7,339 7,331 7,319 7,311 7,303 7,299 7,295 7,290 7,281 7,273 7,260 3,388 3,435 3,448 3,468 3,481 3,495 3,512 3,528 3,546 3,564 3,586 3,597 3,620 4,150 4,165 4,183 4,198 4,300 4,439 4,464 4,471 4,479 4,485 4,524 4,537 4,564 4,574 4,611 4,620 4,633 4,652 4,664 4,702 4,835 4,875 2,369 7,5 7 6,5 6 5,5 1 H NMR (300 MHz, CDCl 3) of compound 9 5 4,5 4 3,5 3 2,5 2
S29 194,445 127,598 127,641 127,685 127,743 127,918 127,983 128,339 128,368 128,397 138,003 138,112 138,454 98,882 68,109 70,596 72,123 73,548 73,825 76,428 76,617 77,039 77,460 77,591 55,377 47,400 30,959 200 190 180 170 160 150 13 C NMR (75 MHz, CDCl 3) of compound 9 140 130 120 110 100 90 80 70 60 50 40 30 20
6,0 2,9 3,1 S30 1 0,5 15,7 7,176 7,198 7,213 7,219 7,226 7,242 7,250 7,260 7,269 7,276 7,288 7,298 7,303 7,309 7,315 7,335 7,341 3,312 3,539 3,552 3,559 3,831 3,843 3,864 3,876 3,926 3,940 3,959 3,973 4,115 4,122 4,437 4,476 4,501 4,541 4,569 4,579 4,611 4,620 4,758 4,798 1,591 1,610 8 7,5 7 6,5 6 5,5 1 H NMR (300 MHz, CDCl 3) of compound 10 5 4,5 4 3,5 3 2,5 2 1,5
S31 137,901 138,213 138,431 127,648 127,706 127,997 128,324 128,382 98,867 70,421 71,868 73,569 73,707 75,489 76,594 76,841 77,016 77,445 67,643 55,230 42,949 140 130 120 110 13 C NMR (75 MHz, CDCl 3) of compound 10 100 90 80 70 60 50 40 30
2,0 2,9 S32 6,3 7,220 7,242 7,260 7,267 7,292 7,308 7,314 7,335 5,513 5,523 5,536 5,545 5,608 5,614 5,632 5,638 3,526 3,682 3,713 3,719 3,751 3,835 3,867 3,880 3,909 3,957 4,002 4,113 4,134 4,154 4,176 4,402 4,408 4,433 4,439 4,442 4,452 05 16 44 56 2,482 6,0 2,020 2,042 2,070 2,111 2,152 2,169 2,175 1,572 7 7,5 6,5 6 5,5 1 H NMR (300 MHz, CDCl 3) of compound 12 5 4,5 4 3,5 3 2,5 2 1,5
S33 168,133 170,075 170,533 170,737 171,784 153,363 136,251 127,269 128,447 129,087 83,619 69,751 72,311 75,787 76,587 76,791 77,016 77,438 62,936 59,286 502 36,457 33,236 20,763 20,967 21,250 24,705 170 160 150 140 130 120 110 13 C NMR (75 MHz, CDCl 3) of compound 12 100 90 80 70 60 50 40 30 20 10 0
S34 7,2 2,0 2,0 1,915 2,019 2,027 2,041 2,071 2,129 2,212 2,242 2,257 2,289 2,330 2,375 2,996 11 35 50 74 90 3,670 3,713 3,763 3,805 3,852 3,880 3,917 3,968 3,991 4,009 4,032 4,106 4,119 4,126 4,130 4,153 4,160 4,405 4,413 4,446 4,454 5,097 5,130 5,170 5,178 5,192 5,198 5,214 5,222 5,295 5,302 5,315 5,322 7,237 7,251 7,260 7,266 7,279 7,293 7,302 7,306 7,310 7,317 1,5 2 2,5 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 1 H NMR (300 MHz, CDCl 3) of compound 13
S35 169,656 170,325 170,383 170,449 170,747 138,010 127,205 128,616 129,037 94,309 76,610 77,031 77,453 68,473 70,814 71,738 62,765 53,486 48,643 42,753 38,340 34,108 20,808 20,910 219 23,338 170 160 150 140 130 120 13 C NMR (75 MHz, CDCl 3) of compound 13 110 100 90 80 70 60 50 40 30 20 10 0
4,0 7,0 S36 1,9 7,260 7,433 7,440 7,455 7,462 2,0 6,846 6,853 6,868 6,875 5,304 5,316 5,325 5,325 5,337 5,347 5,510 5,515 5,530 5,535 51 63 91 3,103 3,543 3,574 3,580 3,612 3,622 3,816 3,897 3,909 3,935 3,939 3,947 3,951 3,977 3,989 4,157 4,180 4,198 4,220 4,292 4,297 4,323 4,328 4,388 4,397 4,428 4,438 2,449 2,043 2,065 2,068 2,084 2,125 2,159 7,5 7 6,5 6 1 H NMR (300 MHz, CDCl 3) of compound 14 5,5 5 4,5 4 3,5 3 2,5 2 1,5
S37 168,208 170,019 170,244 170,702 171,924 161,373 153,425 138,431 118,747 114,493 87,676 70,639 72,602 75,794 76,594 77,016 77,321 77,445 62,575 59,143 593 55,354 36,455 20,836 20,916 269 24,690 170 160 150 140 130 120 13 C NMR (75 MHz, CDCl 3) of compound 14 110 100 90 80 70 60 50 40 30 20 10
1,2 3,9 2,8 6,9 2,9 S38 1 0,5 0 0,8 7,260 2,987 2,999 28 40 3,641 3,673 3,678 3,710 3,813 3,828 3,842 3,859 3,866 3,870 3,896 3,908 4,082 4,103 4,123 4,144 4,344 4,353 4,385 4,394 4,493 4,496 4,497 4,524 4,528 5,400 5,410 5,425 5,430 5,434 5,446 5,455 5,562 5,562 5,566 5,587 5,591 2,483 2,028 2,037 2,103 2,119 2,142 2,156 2,185 8,9 1,372 7 6,5 1 H NMR (300 MHz, CDCl 3) of compound 15 6 5,5 5 4,5 4 3,5 3 2,5 2 1,5
S39 169,689 170,315 170,657 171,886 153,443 85,307 70,071 72,085 75,489 76,594 76,681 77,016 77,438 62,573 59,526 597 48,479 38,508 31,643 20,720 20,923 21,134 24,778 180 170 160 150 140 130 120 13 C NMR (75 MHz, CDCl 3) of compound 15 110 100 90 80 70 60 50 40 30 20 10
S40 14,9 4,0 1,1 2,0 1,1 6,0 2,0 1,959 2,017 2,045 2,052 2,094 2,127 2,143 2,485 2,988 01 28 38 3,382 3,475 3,487 3,506 3,518 3,619 3,652 3,655 3,688 3,737 3,830 3,839 3,850 3,863 3,872 3,891 3,900 3,963 3,975 3,989 4,010 4,021 4,038 4,060 4,080 4,274 4,277 4,304 4,311 4,344 4,354 4,612 4,624 4,646 4,687 4,737 4,754 4,774 4,794 4,823 4,835 4,862 5,007 5,043 5,396 5,405 5,415 5,425 5,434 5,444 5,628 5,632 5,657 5,661 7,245 7,260 7,278 7,302 7,318 7,324 7,332 7,342 7,364 7,376 7,394 7,402 1,5 2 2,5 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 1 H NMR (300 MHz, CDCl 3) of compound 16
S41 168,729 169,980 170,039 170,657 171,617 153,334 138,403 138,760 138,978 127,422 127,465 127,742 127,974 128,171 128,353 98,877 59,315 62,653 68,551 69,838 71,489 72,914 73,620 74,885 75,918 75,983 76,063 76,594 77,016 77,249 77,438 79,030 82,689 55,395 575 36,399 30,014 20,712 20,996 21,381 24,698 170 160 150 140 130 120 13 C NMR (75 MHz, CDCl 3) of compound 16 110 100 90 80 70 60 50 40 30 20 10
S42 4,0 3,8 2,0 2,0 1,9 7,7 2,9 2,8 2,8 1,461 1,600 2,044 2,085 2,092 2,127 2,205 2,446 2,903 2,914 2,943 2,954 3,478 3,504 3,510 3,516 3,548 3,662 3,673 3,770 3,786 3,812 3,823 3,861 3,872 3,900 3,911 4,041 4,046 4,076 4,082 4,087 4,098 4,116 4,139 4,266 4,271 4,297 4,303 4,334 4,339 4,375 4,380 4,489 4,498 4,531 4,539 4,887 4,913 5,200 5,226 5,239 5,265 5,296 5,461 5,522 5,527 5,554 5,560 5,616 5,625 5,639 5,647 7,260 7,344 7,354 7,360 7,368 7,380 7,396 7,432 7,456 7,482 7,526 7,532 7,539 7,544 7,549 7,559 7,568 8,151 8,156 8,179 1 1,5 2 2,5 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 8 1 H NMR (300 MHz, CDCl 3) of compound 17
S43 165,983 169,394 170,121 170,361 170,775 171,742 153,156 126,295 128,128 128,331 128,942 130,251 130,447 133,109 137,559 101,492 102,685 56,656 58,924 63,455 67,723 68,036 68,959 69,177 71,213 75,794 75,809 75,845 76,594 77,016 77,438 81,735 53,129 45,712 35,946 20,378 20,851 21,571 24,639 170 160 150 140 130 120 13 C NMR (75 MHz, CDCl 3) of compound 17 110 100 90 80 70 60 50 40 30 20 10
S44 6,0 2,0 4,0 16,7 2,0 8,0 2,0 1,988 2,123 2,479 2,722 2,764 2,767 2,782 3,170 3,202 3,207 3,239 3,393 3,691 3,697 3,707 3,739 3,752 3,766 3,776 3,781 3,977 3,997 4,018 4,038 4,116 4,130 4,149 4,163 4,281 4,291 4,321 4,331 4,423 4,427 4,455 4,459 4,591 4,601 4,607 4,640 4,647 4,652 4,745 4,750 4,783 4,789 4,958 4,996 5,337 5,347 5,357 5,366 5,376 5,385 5,395 5,524 5,529 5,554 5,557 5,557 7,242 7,253 7,260 7,267 7,272 7,281 7,283 7,293 7,300 7,307 7,316 7,324 7,337 7,343 7,347 7,357 0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 8 8,5 9 1 H NMR (300 MHz, CDCl 3) of compound 18
S45 169,306 169,459 169,873 170,513 172,033 153,367 127,139 127,379 127,844 127,866 128,004 128,244 128,273 128,389 128,484 138,111 138,228 138,620 98,031 58,575 62,677 68,865 70,246 71,599 71,948 73,191 73,264 74,471 75,344 76,594 76,660 77,016 77,438 78,914 82,339 53,194 55,201 48,010 38,513 20,662 20,858 21,127 24,668 180 170 160 150 140 130 120 13 C NMR (75 MHz, CDCl 3) of compound 18 110 100 90 80 70 60 50 40 30 20 10
S46 6,0 6,0 2,6 15,0 2,0 1,795 1,833 1,838 1,876 2,036 2,765 2,781 2,807 2,824 2,829 2,844 2,867 3,329 3,334 3,340 3,345 3,351 3,415 3,463 3,467 3,497 3,502 3,543 3,547 3,574 3,577 3,663 3,677 3,678 3,686 3,698 3,715 3,830 3,839 3,847 3,960 3,968 4,237 4,608 4,645 4,702 4,715 4,760 4,807 4,830 4,870 4,944 4,981 7,297 7,311 7,315 7,325 7,339 7,343 7,350 7,363 7,370 7,393 7,397 7,437 7,440 7,462 1,5 2 2,5 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 1 H NMR (300 MHz, CD 3OD) of compound 19
S47 175,154 171,969 128,594 128,696 128,841 129,241 129,285 129,336 129,358 129,379 139,734 140,010 140,105 99,952 64,452 68,902 69,862 71,295 72,480 73,883 74,334 76,166 76,915 77,359 77,417 80,202 85,110 42,136 48,433 48,716 49,000 49,284 49,567 53,647 53,748 55,872 31,308 22,677 180 170 160 150 13 C NMR (75 MHz, CD 3OD) of compound 19 140 130 120 110 100 90 80 70 60 50 40 30 20
4,0 4,0 2,0 S48 1,6 1,4 4,780 4,433 4,447 3,368 3,374 3,385 3,399 3,584 3,597 3,657 3,660 3,663 3,675 3,678 3,681 3,687 3,741 3,746 3,757 3,764 3,775 3,866 3,867 3,871 3,872 3,880 3,886 3,900 3,908 3,920 2,822 2,831 2,847 2,857 2,5 2,054 1,866 1,891 1,914 5,2 5 4,8 4,6 4,4 1 H NMR (300 MHz, D 2O) of compound 20 4,2 4 3,8 3,6 3,4 3,2 3 2,8 2,6 2,4 2,2 2 1,8