*3.6. Methyl 2,4,6-Tri-O-Benzyl-3-Deoxy-3-C-Methoxymethyl-*β*-*d*-Gulopyranoside* **16**

Compound **14a** (57 mg, 0.12 mmol) was stirred in a 5 mL round-bottom flask in dry THF (2 mL) for 5 min at 0 ◦C. Into the solution, NaH (6 mg, 0.24 mmol) was added and the stirring was continued at 0 ◦C for 5 min. Then, into the reaction mixture iodomethane dropwise was added and the reaction temperature increased to rt gradually. Stirring continued overnight when the TLC showed almost complete consumption of the starting material (TLC heptane/EtOAc, 3:2, R<sup>f</sup> 0.53). Then, NaH was quenched with EtOAc and the volatiles were removed under reduced pressure. The residue was subjected to column chromatography (heptane/EtOAc, 6:1 to 3:1) to provide the purified product **16** (46 mg, 0.09 mmol, 78%). [α] 25 <sup>D</sup> <sup>−</sup>62.5 (c 1.2, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.35–7.20 (m, 15H, Ar*H*), 4.76 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.58 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.57 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.53 (d, 1H, *J*1,2 6.4 Hz, H-1), 4.48 (d, 2H, *J* 12.4 Hz, C*H*2Ph), 4.37 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.11–4.07 (m, 1H, H-5), 3.75–3.71 (m, 3H, H-2, H-4, H-6a), 3.67–3.61 (m, 2H, H-6b, C*H*2OCH3), 3.56–3.50 (m, 4H, C*H*2OCH3, OC*H*3), 3.29 (s, 3H, CH2OC*H*3), 2.58–2.52 (m, 3H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 138.8, 138.43, 138.39, 128.5, 128.43, 128.36, 128.1, 127.94, 128.90, 127.8, 127.74, 127.69, 127.66, 101.8, 75.1, 74.7, 73.7, 73.3, 73.2, 71.8, 70.2, 69.2, 59.0, 56.4, 40.2. HRMS calcd for C17H21NO6+H<sup>+</sup> (M+H)+: 335.1369, found: 335.1369.

#### *3.7. Methyl 2,4,6-Tri-O-Benzyl-3-Deoxy-3-C-Azidomethyl-*β*-*d*-Gulopyranoside* **17**

Into a stirred solution of **14a** (1.6 g, 3.35 mmol) in DCM (25 mL) containing Et3N (890 µL, 6.69 mmol) at 0 ◦C MsCl (390 µL, 5.02 mmol) was added dropwise over 5 min, and the solution was stirred for 4 h at rt (TLC heptane/EtOAc, 1:1, R<sup>f</sup> 0.31). The solution was extracted with 1N HCl (2 × 50 mL) followed by sat'd NaHCO<sup>3</sup> (2 × 50 mL), and the organic layer was dried (Na2SO4). The solvent was removed by rotary evaporation to give a yellow liquid that was dissolved in dry DMF (10 mL). Sodium azide (1.3 g, 20.08 mmol) was added and the solution was heated at 80 ◦C for 6 h to give a yellowish-brown mixture. The mixture was cooled at rt, water (50 mL) was added, and the mixture was extracted with EtOAc (2 × 40 mL). The organic layer was washed with brine (50 mL) and dried (Na2SO4). The solvent was removed by rotary evaporation to give a yellow liquid that was then purified by flash chromatography (Heptane/EtOAc 8:1 to 3:1) to give compound **17** (1.4 g, 2.78 mmol, 83% from **14a**) as a colorless liquid. [α] 25 <sup>D</sup> <sup>−</sup>5.2 (c 0.8, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.38–7.20 (m, 15H, Ar*H*), 4.76 (d, 1H, *<sup>J</sup>* 12.0 Hz, C*H*2Ph), 4.56 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.55 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.51 (d, 1H, *J*1,2 6.4 Hz, H-1), 4.48 (d, 1H, *J* 12.4 Hz, C*H*2Ph), 4.44 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.41 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.09–4.05 (m, 1H, H-5), 3.77–3.64 (m, 5H, H-2, H-4, H-6a, H-6b, C*H*2N3), 3.50 (s, 3H, OC*H*3), 3.39 (dd, 1H, *J* 12.4 Hz, *J* 8.4 Hz, C*H*2N3), 2.42–2.36 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 138.4, 138.3, 137.9, 128.53, 128.52, 128.50, 128.2, 128.02, 127.95, 127.9, 127.8, 100.8, 75.0, 73.7, 73.6, 73.4, 72.5, 72.0, 69.6, 56.4, 48.6, 39.7. HRMS calcd for C29H33N3O5+NH<sup>4</sup> <sup>+</sup> (M+NH4) <sup>+</sup>: 521.2764, found: 521.2775.

#### *3.8. Methyl 2,4,6-Tri-O-Benzyl-3-Deoxy-3-C-[4-(3-Fluorophenyl)-1H-1,2,3-Triazol-1-Yl-Methyl]* β*-*d*-Gulopyranoside* **18**

A solution of azide **17** (53 mg, 0.10 mmol) in dichloromethane (2 mL), 1-Ethynyl-3-fluorobenzene (18.1 µL, 0.16 mmol), CuI (10 mol%, 2 mg) and DIPEA (28 µL, 0.16 mmol) were added and the mixture was stirred at room temperature for 48 h (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.58). The solvent was removed under reduced pressure, and the residue was dissolved in EtOAc (10 mL) and the solution was washed with sat. NH4Cl (10 mL), brine (10 mL), dried over Na2SO<sup>4</sup> and concentrated in vacuo. The product was purified by flash column chromatography (heptane/EtOAc, 6:1 to 1:1) to give the corresponding triazole, **18** as white amorphous solid (56.4 mg, 0.09 mmol, 86%). [α] 25 <sup>D</sup> <sup>−</sup>63 (c 0.6, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.52–7.04 (m, 20H, Ar*H*), 4.80 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.63 (dd, 1H, *J* 6.8 Hz, *J* 14.0 Hz, H-30 ), 4.60–4.44 (m, 7H, H-1, H-30 , C*H*2Ph), 4.35 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.26–4.22 (m, 1H, H-5), 3.79 (dd, 1H, *J* 10.0 Hz, *J* 7.2 Hz, H-6a), 3.74 (dd, 1H, *J* 6.4 Hz, *J* 3.2 Hz, H-4), 3.71 (dd, 1H, *J* 10.0 Hz, *J* 5.2 Hz, H-6b), 3.79 (t, 1H, *J* 4.8 Hz, H-2), 3.51 (s, 1H, OC*H*3), 2.68–2.61 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 163.3 (d, *J* 244 Hz), 146.8, 138.19, 138.16, 137.4, 132.8 (d, *J* 8.3 Hz), 130.5 (d, *J* 8.4 Hz), 128.7, 128.52, 128.51, 128.3, 128.2, 128.0, 127.9, 127.8, 121.3 (d, *J* 2.7 Hz), 120.6, 115.0 (d, *J* 22 Hz), 112.7 (d, *J* 23 Hz), 100.1, 75.2, 73.52, 73.47, 73.1, 72.5, 72.2, 69.4, 56.4, 47.4, 41.1. <sup>19</sup>F NMR (CDCl3, 376 MHz): <sup>−</sup>112.7. HRMS calcd for C37H38FN3O5+H<sup>+</sup> (M+H)+: 624.2874, found: 624.2884.

#### *3.9. Methyl 2,4,6-Tri-O-Benzyl-3-Deoxy-3-C-(Aminomethyl)-*β*-*d*-Gulopyranoside* **19**

Into a stirred solution of **17** (1.31 g, 2.60 mmol) in dry THF (20 mL) at 0 ◦C, LiAlH<sup>4</sup> (148 mg, 3.9 mmol) was added in portions over 5 min under nitrogen atmosphere, and the solution was stirred for 1 h at rt (TLC DCM/MeOH, 15:1, R<sup>f</sup> 0.44). After 30 min, TLC was checked which shows complete conversion of the azide into amine. Then, the reaction was quenched EtOAc and the reaction mixture was filtered through a pad of Celite® (St. Louis, MO, USA). Then, the filtrate was concentrated in vacuo and the crude was purified by column chromatography (DCM:MeOH 25:1) to give compound **19** (969 mg, 2.03 mmol, yield 78%) as a colorless oil. [α] 25 <sup>D</sup> <sup>−</sup>36.2 (c 1.1, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.35–7.22 (m, 15H, Ar*H*), 4.80 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.57–4.54 (m, 3H, H-1, C*H*2Ph), 4.51 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.47 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.42 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 3.97–3.93 (m, 1H, H-5), 3.74–3.65 (m, 4H, H-2, H-4, H-6a, H-6b), 3.52 (s, 3H, OC*H*3), 3.08 (dd, 1H, *J* 6.4 Hz, *J* 12.8 Hz, C*H*2NH2), 2.68 (dd, 1H, *J* 12.8 Hz, *J* 6.4 Hz, C*H*2NH2), 2.32–2.27 (m, 1H, H-3), 1.99 (bs, 2H, CH2N*H*2). <sup>13</sup>C NMR (CDCl3, 100 MHz): 138.6, 138.3, 138.1, 128.53, 128.49, 128.4, 128.2, 128.0, 127.9, 127.83, 127.81, 127.77, 101.3, 76.2, 75.2, 73.6, 73.4, 72.9, 71.7, 69.7, 56.4, 42.7, 39.7. HRMS calcd for C29H35NO5+H<sup>+</sup> (M+H)+: 478.2593, found: 478.2603.

#### *3.10. Methyl 2,4,6-Tri-O-Benzyl-3-Deoxy-3-C-(3-Fluorophenylureidomethyl)-*β*-*d*-Gulopyranoside* **20**

A solution of amine **19** (61 mg, 0.13 mmol) in dry dichloromethane (2 mL), Et3N (35.6 µL, 0.26 mmol) was added and the mixture was stirred at room temperature for 5 min under N<sup>2</sup> atmosphere. Then into the solution phenyl isocyanate (29.2 µL, 0.26 mmol) was added and the solution was stirred at rt for 12 h (TLC heptane/EtOAc, 1:1, R<sup>f</sup> 0.32). The solvent was removed under reduced pressure, and the residue was dissolved in EtOAc (10 mL) and the solution was washed with brine (10 mL), dried over Na2SO<sup>4</sup> and concentrated in vacuo. The product was purified by flash column chromatography (heptane/EtOAc, 5:1 to 2:1) to give the corresponding semicarbazide **20** as a colorless oil (53.4 mg, 0.09 mmol, yield 68%). [α] 25 <sup>D</sup> <sup>−</sup>83.1 (c 0.8, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.39–7.12 (m, 17H, Ar*H*), 6.85 (dd, 1H, *J* 1.2 Hz, *J* 8.0 Hz, Ar*H*), 6.71–6.66 (m, 1H, Ar*H*), 6.11 (bs, 1H, NHCON*H*C6H4F), 5.30 (bs, 1H, N*H*CONHC6H4F), 4.79 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.59 (d, 1H, *J* 6.0 Hz, H-1), 4.55 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.49 (d, 1H, *J* 12.4 Hz, C*H*2Ph), 4.48–4.42 (m, 3H, C*H*2Ph), 4.03–3.99 (m, 1H, H-5), 3.74–3.65 (m, 4H, H-2, H-4, H-6a, H-6b), 3.51 (s, 1H, OC*H*3), 3.42 (dd, 1H, *J* 14.0 Hz, *J* 5.6 Hz, C*H*2NHCON*H*C6H4F), 3.34 (dd, 1H, *J* 14.0 Hz, *J* 7.6 Hz, C*H*2NHCON*H*C6H4F), 2.42–2.36 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 163.3 (d, *J* 243 Hz), 154.9, 140.6 (d, *J* 11 Hz), 138.4, 138.2, 137.9, 130.2 (d, *J* 9.5 Hz), 128.8, 128.5, 128.3, 128.2, 128.0, 127.9, 127.8, 114.8 (d, *J* 2.7 Hz), 109.7 (d, *J* 21.2 Hz), 106.9 (d, *J* 26 Hz), 100.7, 75.3, 73.54, 73.49, 73.0, 72.1, 69.4, 56.5, 39.8, 39.1. <sup>19</sup>F NMR (CDCl3, 376 MHz): <sup>−</sup>111.6. HRMS calcd for C36H40FN2O6+H<sup>+</sup> (M+H)+: 615.2886, found: 615.2870.

#### *3.11. General Procedure for the Synthesis of Amides* **21***,* **22a***–***22l***, and* **23**

To a solution of the amine (1 eq) in dry DCM (2 mL per 0.1 mmol) Et3N (2 eq) was added. Into the solution, acid chloride or anhydride (1.5 eq) was added and the solution was stirred at rt for 8 h. After that, 1(N) HCl solution was added to the reaction mixture and extracted with DCM and washed successively with saturated NaHCO3. After evaporating the solvents in vacuo, the crude material thus obtained was purified by flash chromatography using heptane–EtOAc (5:1 to 1:1) to give pure amides as colorless oils.

#### 3.11.1. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-Phenylsulfonamidomethyl-β-d-Gulopyranoside **21**

Compound **21** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.21) was prepared according to the general procedure 3.11 from the amine **19** (55 mg, 0.12 mmol). Obtained as a colorless oil in 65% yield (46.2 mg, 0.07 mmol). [α] 25 <sup>D</sup> <sup>−</sup>55.7 (c 0.7, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.73–7.17 (m, 20H, Ar*H*), 5.23 (dd, 1H, *<sup>J</sup>* 5.2 Hz, *J* 6.8 Hz, CH2N*H*SO), 4.75 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.53 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.50 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.45 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.42 (d, 1H, *J* 6.0 Hz, H-1), 4.39 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.36 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 3.90–3.87 (m, 1H, H-5), 3.70–3.60 (m, 4H, H-2, H-4, H-6a, H-6b), 3.47 (s, 3H, OC*H*3), 3.17–3.10 (m, 1H, C*H*2NHSO), 3.00–2.93 (m, 1H, C*H*2NHSO), 2.41–2.35 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 139.7, 138.1, 137.9, 137.6, 132.6, 129.1, 128.7, 128.5, 128.2, 128.1, 127.94, 127.91, 127.8, 127.1, 100.5, 76.3, 74.8, 73.54, 73.50, 72.8, 71.8, 69.3, 56.3, 42.2, 39.1. HRMS calcd for C35H39NO7S+NH<sup>4</sup> <sup>+</sup> (M+NH4) <sup>+</sup>: 635.2788, found: 635.2791.

#### 3.11.2. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(Benzamidomethyl)-β-d-Gulopyranoside **22a**

Compound **22a** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.27) was prepared according to the general procedure *3.11* from the amine **19** (43 mg, 0.09 mmol). Obtained as a colorless oil in 70% yield (37 mg, 0.06 mmol). [α] 25 <sup>D</sup> <sup>−</sup>42.4 (c 0.8, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.43–7.22 (m, 20H, Ar*H*), 7.03 (t, 1H, *<sup>J</sup>* 5.6 Hz, CH2N*H*CO), 4.89 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.69 (d, 1H, *J*1,2 6.0 Hz, H-1), 4.57 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.55–4.46 (m, 4H, C*H*2Ph), 4.07–4.03 (m, 1H, H-5), 3.82 (dd, 1H, *J*1,2 6.0 Hz, *J*2,3 4.8 Hz, H-2), 3.79–3.68 (m, 4H, H-4, H-6a, H-6b, C*H*2NHCO), 3.60–3.53 (m, 4H, OC*H*3, C*H*2NHCO), 2.51–2.46 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 166.8, 138.3, 138.2, 137.8, 134.2, 131.2, 128.7, 128.53, 128.51, 128.47, 128.3, 128.2, 128.0, 127.8, 126.9, 100.9, 77.9, 75.9, 74.3, 73.5, 73.1, 72.2, 69.4, 56.5, 39.8, 39.3. HRMS calcd for C36H39NO6+H<sup>+</sup> (M+H)+: 582.2856, found: 582.2851.

#### 3.11.3. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(Acetamidomethyl)-β-d-Gulopyranoside **22b**

Compound **22b** (TLC heptane/EtOAc, 1:1, R<sup>f</sup> 0.4) was prepared according to the general procedure *3.11* from the amine **19** (49 mg, 0.10 mmol). Obtained as a colorless oil in 62% yield (33 mg, 0.06 mmol). [α] 25 <sup>D</sup> <sup>−</sup>31.6 (c 0.8, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.39–7.21 (m, 15H, Ar*H*), 6.05 (bs, 1H, N*H*COCH3), 4.83 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.59 (d, 1H, *J*1,2 6.4 Hz, H-1), 4.55 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.52–4.42 (m, 4H, C*H*2Ph), 3.98 (td, 1H, *J* 6.0 Hz, *J* 2.8 Hz, H-5), 3.74–3.64 (m, 4H, H-2, H-4, H-6a, H-6b), 3.53 (s, 3H, OCH3), 3.51–3.45 (m, 1H, C*H*2NHCO), 3.32–3.26 (s, 1H, C*H*2NHCO), 2.36–2.30 (m, 1H, H-3), 1.74 (s, 3H, NHCOC*H*3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 169.9, 138.4, 138.3, 137.9, 128.7, 128.5, 128.2, 128.12, 128.09, 127.94, 127.86, 127.7, 100.8, 77.1, 75.4, 73.8, 73.5, 73.0, 72.0, 69.4, 56.5, 39.7, 38.4, 23.2. HRMS calcd for C31H37NO6+H<sup>+</sup> (M+H)+: 520.2699, found: 520.2704.

#### 3.11.4. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(2-Fluorobenzamidomethyl)-β-d-Gulopyranoside **22c**

Compound **22c** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.19) was prepared according to the general procedure *3.11* from the amine **19** (49 mg, 0.10 mmol). Obtained as a colorless oil in 59% yield (31.5 mg, 0.06 mmol). [α] 25 <sup>D</sup> <sup>−</sup>41.7 (c 0.7, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 8.05–8.01 (td, 1H, *<sup>J</sup>* 8.0 Hz, *<sup>J</sup>* 1.6 Hz, Ar*H*), 7.48–7.43 (m, 1H, Ar*H*), 7.36–7.16 (m, 17H, Ar*H*), 7.07–7.02 (m, 1H, Ar*H*), 4.84 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.65 (d, 1H, *J*1,2 6.8 Hz, H-1), 4.62 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.57 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.48 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.46 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.40 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.07 (td, 1H, *J* 6.0 Hz, *J* 2.8 Hz, H-5), 3.79–3.58 (m, 6H, H-2, H-4, H-6a, H-6b, C*H*2NHCO), 3.54 (s, 3H, OC*H*3), 2.49–2.43 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 163.2 (d, *J* 3.0 Hz), 160.6 (d, *J* 247 Hz), 138.3, 138.2, 137.8, 133.1 (d, *J* 9.0 Hz), 132.0 (d, *J* 2.0 Hz), 128.46, 128.45, 128.4, 128.3, 128.2, 127.9, 127.8, 127.7, 124.7 (d, *J* 3.1 Hz), 121.4 (d, *J* 12 Hz), 116.1 (d, *J* 24 Hz), 101.0, 76.3, 75.1, 73.6, 73.5, 72.9, 72.0, 69.5, 56.5, 40.0, 38.5. <sup>19</sup>F NMR (CDCl3, 376 MHz): -113.4. HRMS calcd for C36H38FNO6+NH<sup>4</sup> <sup>+</sup> (M+NH4) <sup>+</sup>: 617.3027, found: 617.3025.

3.11.5. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(3-Fluorobenzamidomethyl)-β-d-Gulopyranoside **22d**

Compound **22d** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.24) was prepared according to the general procedure *3.11* from the amine **19** (46 mg, 0.10 mmol). Obtained as a colorless oil in 67% yield (48 mg, 0.06 mmol). [α] 25 <sup>D</sup> <sup>−</sup>61.8 (c 0.7, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.36–6.99 (m, 20H, N*H*CO, Ar*H*), 4.89 (d, 1H, *<sup>J</sup>* 11.2 Hz, C*H*2Ph), 4.69 (d, 1H, *J*1,2 6.0 Hz, H-1), 4.58 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.54–4.47 (m, 4H, C*H*2Ph), 4.07 (td, 1H, *J* 6.4 Hz, *J* 2.8 Hz, H-5), 3.82 (dd, 1H, *J*1,2 6.0 Hz, *J*2,3 4.8 Hz, H-2), 3.81–3.66 (m, 4H, H-4, H-6a, H-6b, C*H*2NHCO), 3.60–3.54 (m, 4H, C*H*2NHCO, OC*H*3), 2.50–2.44 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 165.5 (d, *J* 2.2 Hz), 162.7 (d, *J* 246 Hz), 138.2, 138.0, 137.7, 136.6 (d, *J* 6.8 Hz), 130.0 (d, *J* 7.8 Hz), 128.7, 128.53, 128.50, 128.4, 128.29, 128.25, 128.0, 127.9, 127.8, 122.1 (d, *J* 3.0 Hz), 118.2 (d, *J* 22 Hz), 114.4 (d, *J* 23 Hz), 100.8, 78.8, 75.8, 74.3, 73.5, 73.0, 72.2, 69.3, 56.5, 39.6, 39.5. <sup>19</sup>F NMR (CDCl3, 376 MHz): <sup>−</sup>111.9. HRMS calcd for C36H38FNO6+H<sup>+</sup> (M+H)+: 600.2761, found: 600.2772.

3.11.6. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(4-Fluorobenzamidomethyl)-β-d-Gulopyranoside **22e**

Compound **22e** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.2) was prepared according to the general procedure *3.11* from the amine **19** (51 mg, 0.11 mmol). Obtained as a colorless oil in 71% yield (45.4 mg, 0.08 mmol). [α] 25 <sup>D</sup> +51.9 (c 0.6, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.36–7.23 (m, 17H, Ar*H*), 7.05 (t, 1H, *J* 5.6 Hz, N*H*CO), 6.89–6.84 (m, 2H, Ar*H*), 4.90 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.70 (d, 1H, *J*1,2 6.0 Hz, H-1), 4.58 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.54–4.48 (m, 4H, C*H*2Ph), 4.05 (td, 1H, *J* 6.0 Hz, *J* 2.8 Hz, H-5), 3.83 (dd, 1H, *J*1,2 6.0 Hz, *J*2,3 4.8 Hz, H-2), 3.80–3.67 (m, 4H, H-4, H-6a, H-6b, C*H*2NHCO), 3.59–3.52 (m, 4H, C*H*2NHCO, OC*H*3), 2.52–2.46 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 165.7, 164.5 (d, *J* 250 Hz), 138.2, 138.1, 130.3 (d, *J* 3.0 Hz), 129.1 (d, *J* 8.9 Hz), 128.8, 128.6, 128.53, 128.52, 128.33, 128.28, 128.0, 127.9, 127.8, 115.4 (d, *J* 22 Hz), 100.8, 78.1, 76.0, 74.4, 73.5, 73.1, 72.2, 69.3, 56.5, 39.61, 39.58. <sup>19</sup>F NMR (CDCl3, 376 MHz): −108.8. HRMS calcd for C36H38FNO6+NH<sup>4</sup> <sup>+</sup> (M+NH4) <sup>+</sup>: 617.3027, found: 617.3038.

3.11.7. Methyl2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(3,4,5-Trifluorobenzamidomethyl) β-d-Gulopyranoside **22f**

Compound **22f**(TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.18) was prepared according to the general procedure *3.11* from the amine **19** (49 mg, 0.10 mmol). Obtained as a colorless oil in 53% yield (34.6 mg, 0.06 mmol). [α] 25 <sup>D</sup> <sup>−</sup>73.6 (c 0.8, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.36–6.93 (m, 18H, Ar*H*), 4.87 (d, 1H, *<sup>J</sup>* 11.2 Hz, C*H*2Ph), 4.68 (d, 1H, *J*1,2 5.6 Hz, H-1), 4.58 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.51–4.48 (m, 4H, C*H*2Ph), 4.07 (td, 1H, *J* 6.4 Hz, *J* 3.6 Hz, H-5), 3.82–3.53 (m, 9H, H-2, H-4, H-6a, H-6b, OC*H*3, C*H*2NHCO), 2.46–2.40 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 163.7, 151.0 (ddd, *J* 3.4 Hz, *J* 10.2 Hz, *J* 251 Hz), 141.9 (dt, *J* 15.2 Hz, *J* 255 Hz), 138.2, 137.9, 137.7, 130.4–130.2 (m), 128.8, 128.6, 128.53, 128.47, 128.29, 128.27, 128.2, 127.90, 127.85, 111.5 (dd, *J* 6.1 Hz, *J* 16 Hz), 100.5, 78.1, 75.8, 74.3, 73.6, 73.0, 72.3, 69.3, 56.5, 40.0, 39.3. <sup>19</sup>F NMR (CDCl3, 376 MHz): -132.1 (d, *<sup>J</sup>* 20 Hz), <sup>−</sup>155.7 (t, *<sup>J</sup>* 20 Hz). HRMS calcd for C36H36F3NO6+NH<sup>4</sup> <sup>+</sup> (M+NH4) <sup>+</sup>: 653.2838, found: 653.2845.

3.11.8. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(2,3,4,5,6-Pentafluorobenzamidomethyl) β-d-Gulopyranoside **22g**

Compound **22g** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.17) was prepared according to the general procedure *3.11* from the amine **19** (45 mg, 0.09 mmol). Obtained as a colorless oil in 49% yield (31 mg, 0.05 mmol). [α] 25 <sup>D</sup> <sup>−</sup>75.7 (c 0.5, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.36–7.20 (m, 15H, Ar*H*), 6.81 (t, 1H, *<sup>J</sup>* 5.6 Hz, CH2N*H*CO), 4.89 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.65 (d, 1H, *J*1,2 6.0 Hz, H-1), 4.57 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.51 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.48 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.47 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.42 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.06 (td, 1H, *J* 6.8 Hz, *J* 3.6 Hz, H-5), 3.81 (dd, 1H, *J*1,2 6.0 Hz, *J*2,3 3.6 Hz, H-2), 3.78–3.69 (m, 3H, H-4, H-6a, H-6b), 3.63–3.58 (m, 2H, C*H*2NHCO), 3.54 (s, 1H, OCH3), 2.45–3.39 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 156.9, 145.1–144.9 (m), 142.6–142.4 (m), 140.9–140.6 (m), 138.8–138.5 (m), 138.2, 137.9, 137.7, 136.3–136.0 (m), 128.5, 128.2, 128.1, 128.0, 127.9, 127.8, 111.9–111.5 (m), 106.4, 100.3, 77.8, 75.4, 73.9, 73.5, 72.4, 69.3, 56.5, 39.8, 38.9. <sup>19</sup>F NMR (CDCl3, 376 MHz): <sup>−</sup>140.5 to −140.6 (m, 2F), −151.7 (t, 1F, *J* 21 Hz), −160.1 to −160.3 (m, 2F). HRMS calcd for C36H34F5NO6+NH<sup>4</sup> + (M+NH4) <sup>+</sup>: 689.2650, found: 689.2656.

3.11.9. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(3-Methoxybenzamidomethyl)-β-d-Gulopyranoside **22h**

Compound **22h** (TLC heptane/EtOAc, 1:1, R<sup>f</sup> 0.45) was prepared according to the general procedure *3.11* from the amine **19** (47 mg, 0.10 mmol). Obtained as a colorless oil in 51% yield (30.7 mg, 0.05 mmol). [α] 25 <sup>D</sup> <sup>−</sup>43.2 (c 0.5, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.35–7.21 (m, 17H, Ar*H*), 7.08 (t, 1H, *<sup>J</sup>* 8.0 Hz, Ar*H*), 7.00 (m, 2H, CH2N*H*CO, Ar*H*), 6.75–6.72 (m, 1H, Ar*H*), 4.87 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.68 (d, 1H, *J*1,2 6.4 Hz, H-1), 4.57 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.54 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.51 (d, 1H, *J* 12.8 Hz, C*H*2Ph), 4.48 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.45 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.05 (td, 1H, *J* 6.4 Hz, *J* 2.8 Hz, H-5), 3.83 (dd, 1H, *J*1,2 6.4 Hz, *J*2,3 5.2 Hz, H-2), 3.79 (s, 3H, C6H4OC*H*3), 3.78–3.67 (m, 5H, H-2, H-4, H-6a, H-6b, C*H*2NHCO), 3.59–3.53 (m, 4H, C*H*2NHCO, OCH3), 2.50–2.45 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 166.8, 159.9, 138.3, 138.2, 137.8, 129.5, 128.7, 128.5, 128.4, 128.3, 128.1, 128.0, 127.9, 127.8, 118.4, 117.7, 112.3, 100.9, 77.6, 75.8, 74.2, 73.5, 73.1, 72.1, 69.4, 56.5, 55.5, 39.8, 39.2. HRMS calcd for C37H41NO7+H<sup>+</sup> (M+H)+: 612.2961, found: 612.2972.

#### 3.11.10. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(p-Toluamidomethyl)-β-d-Gulopyranoside **22i**

Compound **22i** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.24) was prepared according to the general procedure *3.11* from the amine **19** (51 mg, 0.11 mmol). Obtained as a colorless oil in 61% yield (38.8 mg, 0.07 mmol). [α] 25 <sup>D</sup> <sup>−</sup>56.2 (c 0.5, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.35–7.21 (m, 17H, Ar*H*), 7.04 (d, 1H, *<sup>J</sup>* 7.6 Hz, Ar*H*), 6.96 (t, 1H, *J* 6.0 Hz, CH2N*H*CO), 4.88 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.68 (d, 1H, *J*1,2 6.4 Hz, H-1), 4.57 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.53 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.51 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.48 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.45 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.04 (td, 1H, *J* 6.4 Hz, *J* 2.8 Hz, H-5), 3.82 (dd, 1H, *J*1,2 6.4 Hz, *J*2,3 5.2 Hz, H-2), 3.78–3.67 (m, 3H, H-4, H-6a, H-6b, C*H*2NHCO), 3.58–3.52 (m, 4H, C*H*2NHCO, OC*H*3), 2.51–2.45 (m, 1H, H-3), 2.36 (s, 3H, C*H*3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 166.8, 141.6, 138.3, 138.2, 137.9, 131.4, 130.3, 129.24, 129.16, 128.7, 128.52, 128.51, 128.4, 128.3, 128.1, 128.0, 127.9, 127.8, 126.9, 101.0, 77.8, 75.9, 74.2, 73.5, 73.1, 72.1, 69.4, 56.5, 39.9, 39.2, 21.5. HRMS calcd for C37H41NO6+H<sup>+</sup> (M+H)+: 596.3012, found: 596.3019.

3.11.11. Methyl 2,4,6-Tri-*O*-Benzyl-3-Deoxy-3-*C*-(3,5-Dimethoxybenzamidomethyl) β-d-Gulopyranoside **22j**

Compound **22j** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.22) was prepared according to the general procedure *3.11* from the amine **19** (53 mg, 0.11 mmol). Obtained as a colorless oil in 67% yield (48 mg, 0.07 mmol). [α] 25 <sup>D</sup> <sup>−</sup>39.5 (c 0.8, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.35–7.18 (m, 15H, Ar*H*), 6.82 (t, 1H, *<sup>J</sup>* 6.0 Hz, N*H*CO), 6.72 (d, 2H, *J* 2.4 Hz, Ar*H*), 6.54 (t, 1H, *J* 2.4 Hz, Ar*H*), 4.84 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.65 (d, 1H, *J*1,2 6.4 Hz, H-1), 4.57 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.56 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.48 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.47 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.43 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.03 (td, 1H, *J* 6.4 Hz, *J* 2.8 Hz, H-5), 3.78 (dd, 1H, *J*1,2 6.0 Hz, *J*2,3 4.8 Hz, H-2), 3.75–3.65 (m, 10H, H-4, H-6a, H-6b, C*H*2NHCO, <sup>2</sup> <sup>×</sup> OCH3), 3.57–3.52 (m, 4H, C*H*2NHCO, OC*H*3), 2.47–2.41 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 167.1, 160.9, 163.3, 138.3, 138.2, 137.8, 136.8, 128.7, 128.5, 128.2, 128.1, 128.0, 127.93, 127.88, 127.8, 104.9, 103.6, 100.9, 77.2, 75.6, 73.9, 73.5, 73.1, 72.1, 69.5, 56.5, 55.6, 39.9, 39.0. HRMS calcd for C38H43NO8+H<sup>+</sup> (M+H)+: 642.3066, found: 642.3067.

3.11.12. Methyl 2,4,6-tri-*O*-Benzyl-3-Deoxy-3-*C*-(3-Trifluoromethylbenzamidomethyl) β-d-Gulopyranoside **22k**

Compound **22k** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.25) was prepared according to the general procedure *3.11* from the amine **19** (43 mg, 0.09 mmol). Obtained as a colorless oil in 55% yield (32.2 mg, 0.05 mmol). [α] 25 <sup>D</sup> <sup>−</sup>38.7 (c 0.8, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 8.00 (s, 1H, Ar*H*), 7.69–7.66 (m, 1H, Ar*H*), 7.34–7.21 (m, 17H, Ar*H*), 7.09 (t, 1H, *J* 6.0 Hz, CH2N*H*CO), 4.88 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.69 (d, 1H, *J*1,2 6.0 Hz, H-1), 4.58 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.53 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.51–4.47 (m, 3H, C*H*2Ph), 4.07 (s td, 1H, *J* 6.4 Hz, *J* 3.2 Hz, H-5), 3.83 (dd, 1H, *J* 6.0 Hz, *J* 4.8 Hz, H-2), 3.81–3.68 (m, 4H, H-2, H-4, H-6a, H-6b, C*H*2NHCO), 3.62–3.59 (m, 1H, C*H*2NHCO), 3.56 (s, 3H, OC*H*3), 2.50–2.45 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 165.5, 138.2, 138.1, 137.8, 135.1, 133.4 131.2 (q, *J* 32 Hz), 129.5, 129.2, 129.1, 128.7, 128.54, 128.52, 128.4, 128.31, 128.25, 128.0, 127.9, 127.8, 125.2, 124.6 (q, *J* 3.7 Hz), 123.7 (q, *J* 271 Hz), 100.8, 77.8, 75.8, 74.3, 73.6, 73.1, 72.2, 69.3, 56.5, 39.62, 39.61. <sup>19</sup>F NMR (CDCl3, 376 MHz): <sup>−</sup>62.7. HRMS calcd for C37H38F3NO6+H<sup>+</sup> (M+H)+: 650.2729, found: 650.2727.
