3.12.12. Methyl 3-Deoxy-3-*C*-(4-Fluorobenzamidomethyl)-β-d-Galactopyranoside **7e**

Compound **7e** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.44) was prepared according to the general procedure *3.12* from the amide **22e** (40 mg, 0.07 mmol). Obtained as a colorless oil in 53% yield (11.6 mg, 0.04 mmol) from flash column chromatography (DCM:MeOH 20:1–9:1). [α] 25 <sup>D</sup> −16.4 (c 0.5, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 7.89–7.84 (m, 2H, Ar*H*), 7.22–7.16 (m, 2H, Ar*H*), 4.47 (d, 1H, *J*1,2 7.2 Hz, H-1), 3.94 (td, 1H, *J* 6.0 Hz, *J* 3.0 Hz, H-5), 3.88–3.85 (m, 2H, H-2, H-4), 3.78 (d, 1H, *J*6a,6b 11.6 Hz, *J*5,6a 5.6 Hz, H-6a), 3.75 (d, 1H, *J*6a,6b 11.6 Hz, *J*5,6b 5.6 Hz, H-6b), 3.66 (d, 1H, *J* 14.0 Hz, *J* 6.4 Hz, C*H*2NH), 3.61 (d, 1H, *J* 14.0 Hz, *J* 6.4 Hz, C*H*2NH), 3.53 (s, 3H, OC*H*3), 2.40–2.34 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 169.3, 166.2 (d, *J* 249 Hz), 131.9 (d, *J* 3.0 Hz), 130.8 (d, *J* 8.9 Hz), 116.4 (d, *J* 22 Hz), 103.7, 75.9, 69.0, 68.6, 63.1, 56.8, 46.4, 37.8. <sup>19</sup>F NMR (CD3OD, 376 MHz): <sup>−</sup>110.7. HRMS calcd for C15H20FNO6+H<sup>+</sup> (M+H)+: 330.1353, found: 330.1354.

### 3.12.13. Methyl 3-Deoxy-3-*C*-(3,4,5-Trifluorobenzamidomethyl)-β-d-Galactopyranoside **7f**

Compound **7f** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.47) was prepared according to the general procedure *3.12* from the amide **22f**(31 mg, 0.05 mmol). Obtained as a colorless oil in 70% yield (12.5 mg, 0.03 mmol) from flash column chromatography (DCM:MeOH 20:1–9:1). [α] 25 <sup>D</sup> <sup>−</sup>13.5 (c 0.6, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 7.66–7.59 (m, 2H, Ar*H*), 4.45 (d, 1H, *J* 6.8 Hz, H-1), 4.00 (td, 1H, *J* 6.0 Hz, *J* 2.0 Hz, H-5), 3.87–3.84 (m, 2H, H-2, H-4), 3.76 (d, 2H, *J* 5.6 Hz, H-6a, H-6b), 3.66 (dd, 1H, *J* 14.0 Hz, *J* 6.0 Hz, C*H*2NH), 3.59 (dd, 1H, *J* 14.0 Hz, *J* 9.2 Hz, C*H*2NH), 3.53 (s, 3H, OC*H*3), 2.40–2.40–2.34 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 166.7, 152.3 (ddd, 248.3 Hz, *J* 9.8 Hz, *J* 3.8 Hz), 143.0 (dt, *J* 254 Hz, *J* 16 Hz,), 132.2–132.0 (m), 113.1 (dd, *J* 17 Hz, *J* 6.1 Hz), 103.7, 75.9, 68.8, 68.5, 63.1, 56.8, 46.3, 38.0. <sup>19</sup>F NMR (CD3OD, 376 MHz): <sup>−</sup>135.7 (d, *<sup>J</sup>* 20 Hz). <sup>−</sup>159.1 (t, *<sup>J</sup>* 20 Hz). HRMS calcd for C15H18F3NO6+H<sup>+</sup> (M+H)+: 366.1164, found: 366.1161.

#### 3.12.14. Methyl 3-Deoxy-3-*C*-(2,3,4,5,6-Pentafluorobenzamidomethyl)-β-d-Galactopyranoside **7g**

Compound **7g** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.38) was prepared according to the general procedure *3.12* from the amide **22g** (30 mg, 0.04 mmol). Obtained as a colorless oil in 83% yield (14.9 mg, 0.04 mmol) from flash column chromatography (DCM:MeOH 20:1–8:1). [α] 25 <sup>D</sup> −18.9 (c 0.6, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 4.46 (d, 1H, *J* 6.4 Hz, H-1), 3.94–3.85 (m, 4H, H-2, H-4, H-5), 3.79 (dd, 1H, *J* 6.0 Hz, *J* 11.2 Hz, H-6a), 3.79 (dd, 1H, *J* 5.2 Hz, *J* 11.2 Hz, H-6a), 3.68 (dd, 1H, *J* 6.4 Hz, *J* 14.4 Hz, C*H*2NHCO), 3.62 (dd, 1H, *J* 14.4 Hz, *J* 8.8 Hz, C*H*2NHCO), 3.53 (s, 3H, OC*H*3), 2.38–2.32 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 159.9, 146.4, 144.0, 140.2, 137.6, 103.6, 75.8, 68.5, 68.4, 63.2, 56.9, 46.3, 37.7. <sup>19</sup>F NMR (CD3OD, 376 MHz): <sup>−</sup>143.8 to <sup>−</sup>143.2 (m), <sup>−</sup>155.2 to <sup>−</sup>155.3 (m), <sup>−</sup>163.7 to <sup>−</sup>163.9 (m). HRMS calcd for C15H16F5NO6+H<sup>+</sup> (M+H)+: 402.0976, found: 402.0974.

#### 3.12.15. Methyl 3-Deoxy-3-*C*-(3-Methoxybenzamidomethyl)-β-d-Galactopyranoside **7h**

Compound **7h** (TLC, DCM/MeOH, 10:1, R<sup>f</sup> 0.42) was prepared according to the general procedure *3.12* from the amide **22h** (28 mg, 0.03 mmol). Obtained as a colorless oil in 66% yield (10.3 mg, 0.03 mmol) from flash column chromatography (DCM:MeOH 20:1–10:1). [α] 25 <sup>D</sup> −9.5 (c 0.5, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 8.47 (t, *J* 5.2 Hz, CON*H*), 7.38–7.33 (m, 3H, Ar*H*), 7.08 (m, 1H, Ar*H*), 4.47 (d, 1H, *J* 7.2 Hz, H-1), 3.94 (td, 1H, *J* 5.6 Hz, *J* 2.0 Hz, H-5), 3.88–3.85 (m, 2H, H-2, H-4), 3.84 (s, 3H, OCH3), 3.78 (d, 2H, *J* 5.6 Hz, H-6a, H-6b), 3.66–3.62 (m, 2H, C*H*2NN), 3.53 (s, 3H, OC*H*3), 2.41–2.35 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 100 MHz): 170.3, 161.3, 137.0, 130.7, 120.3, 118.5, 113.6, 103.7, 75.9, 70.0, 68.6, 63.1, 56.9, 55.9, 46.4, 37.8. HRMS calcd for C16H23NO7+H<sup>+</sup> (M+H)+: 342.1553, found: 342.1555.
