3.12.7. Methyl 3-Deoxy-3-*C*-(Phenylsufonamido)Methyl-β-d-Galactopyranoside **6**

Compound **6** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.45) was prepared according to the general procedure *3.12* from amide **21** (39 mg, 0.06 mmol). Obtained as a colorless oil in 53% yield (11.6 mg, 0.03 mmol) from flash column chromatography (DCM:MeOH 20:1–10:1). [α] 25 <sup>D</sup> <sup>−</sup>21.4 (c 0.6, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 7.88–7.56 (m, 5H, Ar*H*), 4.26 (d, 1H, *J* 7.2 Hz, H-1), 3.93 (d, 1H, *J* 3.6 Hz, H-4), 3.80 (dd, 1H, *J*1,2 7.2 Hz, *J*2,3 6.0 Hz, H-2), 3.76–3.70 (m, 3H, H-5, H-6a, H-6b), 3.20 (dd, 1H, *J* 5.2 Hz, *J* 11.2 Hz, C*H*2NH), 3.20 (dd, 1H, *J* 11.2 Hz, *J* 10.0 Hz, C*H*2NH), 2.26–2.21 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 141.7, 133.7, 130.3, 128.0, 103.5, 75.7, 68.4, 67.9, 63.2, 56.8, 46.3, 40.6. HRMS calcd for C14H21NO7S+H<sup>+</sup> (M+H)+: 348.1117, found: 348.1115.

### 3.12.8. Methyl 3-Deoxy-3-*C*-Benzamidomethyl-β-d-Gulopyranoside **7a**

Compound **7a** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.41) was prepared according to the general procedure *3.12* from the amide **22a** (35 mg, 0.05 mmol). Obtained as a colorless oil in 59% yield (11 mg, 0.04 mmol) from flash column chromatography (DCM:MeOH 20:1–10:1). [α] 25 <sup>D</sup> <sup>−</sup>6.5 (c 0.6, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 7.82–7.80 (m, 2H, Ar*H*), 7.56–7.52 (m, 1H, Ar*H*), 7.49–7.44 (m, 2H, Ar*H*), 4.48 (d, 1H, *J*1,2 6.8 Hz, H-1), 3.95 (td, 1H, *J* 6.0 Hz, *J* 2.4 Hz, H-5), 3.89–3.86 (m, 2H, H-2, H-4), 3.79 (d, 1H, *J*6a,6b 12.4 Hz, *J*5,6a 5.6 Hz, H-6a), 3.75 (dd, 1H, *J*6a,6b 12.4 Hz, *J*5,6b 5.6 Hz, H-6b), 3.68 (dd, 1H, *J* 14.0 Hz, *J* 6.4 Hz, C*H*2NH), 3.61 (dd, 1H, *J* 11.2 Hz, *J* 6.4 Hz, C*H*2NH), 3.54 (s, 3H, OC*H*3), 2.42–2.35 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 170.5, 135.6, 132.7, 129.6, 128.2, 103.7, 76.0, 69.0, 68.7, 63.1, 56.8, 46.4, 37.8. HRMS calcd for C14H19NO6+H<sup>+</sup> (M+H)+: 289.1291, found: 298.1289.

#### 3.12.9. Methyl 3-Deoxy-3-*C*-Acetamidomethyl-β-d-Gulopyranoside **7b**

Compound **7b** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.42) was prepared according to the general procedure *3.12* from the amide **22b** (27 mg, 0.05 mmol). Obtained as a colorless oil in 75% yield (9.7 mg, 0.04 mmol) from flash column chromatography (DCM:MeOH 15:1–7:1). [α] 25 <sup>D</sup> <sup>−</sup>1.5 (c 0.6, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 4.40 (d, 1H, *J*1,2 6.8 Hz, H-1), 3.88–3.84 (m, 1H, H-5), 3.82–371 (m, 4H, H-2, H-4, H-6a, H-6b), 3.51 (s, 3H, OC*H*3), 3.44 (dd, 1H, *J* 14.0 Hz, *J* 6.0 Hz, C*H*2NH), 3.38 (dd, 1H, *J* 14.0 Hz, *J* 8.8 Hz, C*H*2NH), 2.24–2.18 (m, 1H, H-3), 1.95 (s, 3H, NHCOC*H*3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 173.6, 103.6, 75.9, 68.7, 68.5, 63.1, 56.8, 46.3, 37.1, 22.6. HRMS calcd for C10H19NO6+H<sup>+</sup> (M+H)+: 250.1291, found: 250.1291.

#### 3.12.10. Methyl 3-Deoxy-3-*C*-(2-Fluorobenzamidomethyl)-β-d-Galactopyranoside **7c**

Compound **7c** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.4) was prepared according to the general procedure 3.12 from the amide **22c** (33 mg, 0.06 mmol). Obtained as a colorless oil in 69% yield (12.5 mg, 0.04 mmol) from flash column chromatography (DCM:MeOH 20:1–9:1). [α] 25 <sup>D</sup> −9.3 (c 0.5, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 7.76 (td, 1H, *J* 7.6 Hz, *J* 2.0 Hz, Ar*H*), 7.56–7.50 (m, 1H, Ar*H*), 7.28 (td, 1H, *J* 7.6 Hz, *J* 0.8 Hz, Ar*H*), 7.20 (ddd, 1H, *J* 11.2 Hz, *J* 8.4 Hz, *J* 0.8 Hz, Ar*H*), 4.48 (d, 1H, *J*1,2 7.2 Hz, H-1), 3.93–3.86 (m, 3H, H-2, H-4, H-5), 3.77 (d, 2H, *J*5,6a, *J*5,6b 5.6 Hz, H-6a, H-6b), 3.66 (d, 2H, *J* 7.2 C*H2*NH), 3.53 (s, 3H, OC*H*3), 2.42–2.34 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 166.7, 161.4 (d, *J* 248 Hz), 134.2 (d, *J* 8.8 Hz), 131.6 (d, *J* 2.3 Hz), 125.7 (d, *J* 3.4 Hz), 123.9 (d, *J* 14 Hz), 131.6 (d, *J* 23 Hz), 103.7, 76.0, 69.0, 68.8, 63.1, 56.9, 46.1, 38.1. <sup>19</sup>F NMR (CD3OD, 376 MHz): <sup>−</sup>116.0. HRMS calcd for C15H20FNO6+H<sup>+</sup> (M+H)+: 330.1353, found: 330.1352.

#### 3.12.11. Methyl 3-Deoxy-3-*C*-(3-Fluorobenzamidomethyl)-β-d-Galactopyranoside **7d**

Compound **7d** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.45) was prepared according to the general procedure *3.12* from the amide **22d** (35 mg, 0.06 mmol). Obtained as a colorless oil in 59% yield (11.3 mg, 0.03 mmol) from flash column chromatography (DCM:MeOH 20:1–10:1). [α] 25 <sup>D</sup> −14.6 (c 0.6, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 7.65–7.26 (m, 4H, Ar*H*), 4.47 (d, 1H, *J* 7.2 Hz, H-1), 3.94 (td, 1H, *J* 6.0 Hz, *J* 2.0 Hz, H-5), 3.88–3.85 (m, 2H, H-2, H-4), 3.77 (d, 2H, *J* 5.6 Hz, H-6a, H-6b), 3.67 (dd, 1H, *J* 14.0 Hz, *J*

6.4 Hz, C*H*2OH), 3.67 (dd, 1H, *J* 14.0 Hz, *J* 9.2 Hz, C*H*2OH), 3.53 (s, 3H, OC*H*3), 2.41–2.35 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 168.9 (d, *J* 2.7 Hz), 164.1 (d, *J* 244 Hz), 138.0 (d, *J* 6.8 Hz), 131.6 (d, *J* 7.9 Hz), 124.0 (d, *J* 2.9 Hz), 119.4 (d, *J* 22 Hz), 115.2 (d, *J* 23 Hz), 103.6, 75.9, 68.9, 68.6, 63.1, 56.8, 46.4, 37.8. HRMS calcd for C15H20FNO6+H<sup>+</sup> (M+H)+: 330.1353, found: 330.1354.
