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

Compound **22l** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.32) was prepared according to the general procedure *3.11* from the amine **19** (60 mg, 0.13 mmol). Obtained as a colorless oil in 55% yield (45.5 mg, 0.07 mmol). [α] 25 <sup>D</sup> <sup>−</sup>47.8 (c 0.9, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.61–7.24 (m, 24H, Ar*H*), 7.10 (t, 1H, *<sup>J</sup>* 6.0 Hz, CH2N*H*CO), 4.92 (d, 1H, *J* 11.2 Hz, C*H*2Ph), 4.72 (d, 1H, *J*1,2 6.4 Hz, H-1), 4.59 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.57–4.48 (m, 4H, C*H*2Ph), 4.08 (td, 1H, *J* 6.0 Hz, *J* 2.8 Hz, H-5), 3.85 (dd, 1H, *J*1,2 6.0 Hz, *J*2,3 4.8 Hz, H-2), 3.82–3.70 (m, 4H, H-4, H-6a, H-6b, C*H*2NHCO), 3.64–3.59 (m, 1H, C*H*2NHCO), 3.58 (s, 3H, OC*H*3), 2.55–2.50 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 166.5, 143.9, 140.3, 138.3, 138.2, 137.9, 132.9, 129.0, 128.7, 128.53, 128,49, 128.3, 128.2, 128.02, 127.98, 127.9, 127.8, 127.4, 127.24, 127.15, 100.9, 77.9, 75.9, 74.3, 73.5, 73.1, 72.2, 69.4, 56.5, 39.8, 39.4. HRMS calcd for C42H43NO6+NH<sup>4</sup> <sup>+</sup> (M+NH4) <sup>+</sup>: 675.3434, found: 675.3433.

### 3.11.14. Methyl 2,4,6-tri-*O*-Benzyl-3-Deoxy-3-*C*-(Diphenylphosphonamidomethyl) β-d-Gulopyranoside **23**

Compound **23** (TLC heptane/EtOAc, 2:1, R<sup>f</sup> 0.26) was prepared according to the general procedure *3.11* from the amine **19** (52 mg, 0.11 mmol). Obtained as a colorless oil in 69% yield (53.3 mg, 0.08 mmol). [α] 25 <sup>D</sup> <sup>−</sup>77.8 (c 0.7, CHCl3). <sup>1</sup>H NMR (CDCl3, 400 MHz): 7.36–7.13 (m, 20H, Ar*H*), 4.76 (d, 1H, *<sup>J</sup>* 12.0 Hz, CH2Ph), 4.55–49 (m, 3H, H-1, C*H*2Ph), 4.45 (d, 1H, *J* 12.0 Hz, C*H*2Ph), 4.34 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 4.28 (d, 1H, *J* 11.6 Hz, C*H*2Ph), 3.95–92 (m, 1H, H-5), 3.71–3.58 (m, 5H, H-2, H-4, H-6a, H-6b, N*H*PO(OPh)2), 3.47 (s, 3H, OC*H*3), 3.40–3.31 (m, 1H, C*H*2NHSO), 3.15–3.09 (m, 1H, C*H*2NHSO), 2.33–2.27 (m, 1H, H-3). <sup>13</sup>C NMR (CDCl3, 100 MHz): 150.9 (dd, *J* 6.7 Hz, *J* 2.4 Hz), 138.22, 138.21, 137.9, 128.6, 128.51, 128.45, 128.1, 128.0, 127.93, 127.87, 127.8, 125.0 (d, *J* 4.3 Hz), 120.3 (d, *J* 5.0 Hz, *J* 8.0 Hz), 100.8, 76.1, 74.9, 73.6, 73.4, 72.8, 71.8, 69.5, 56.5, 42.1 (d, *J* 1.8 Hz), 40.2. <sup>31</sup>P NMR (CDCl3, 162 MHz): -1.01. HRMS calcd for C41H44PNO8+H<sup>+</sup> (M+H)+: 710.2883, found: 710.2889.

#### *3.12. General Procedure the Synthesis of* **1a***,* **1b***,* **2–6***,* **7a***–***7l***, and* **8**

A solution of crude in EtOAc/isopropanol (1:3) was stirred with Pd(OH)2/C (10% wt., 1 mg per 4 mg of crude) under hydrogen atmosphere at room temperature for 12 h. All the hydrogenation reactions were carried out in an EtOAc-isopropanol mixture (1:3, 4 mL). After the completion of the reaction (as indicated by TLC), the reaction mixture was filtered through a Celite bed and washed with methanol. The filtrate was concentrated under reduced pressure and purified through the flash column (DCM:MeOH) to get the desired compounds as white amorphous solids or colorless oils.

#### 3.12.1. Methyl 3-Deoxy-3-*C*-Hydroxymethyl-β-d-Gulopyranoside **1a**

Compound **1a** (TLC, DCM/MeOH, 5:1, R<sup>f</sup> 0.41) was prepared according to the general procedure *3.12* from the alcohol **14a** (63 mg, 0.13 mmol). Obtained as a white amorphous solid in 51% yield (14 mg, 0.07 mmol) from flash column chromatography (DCM:MeOH 12:1–5:1). [α] 25 <sup>D</sup> −50.7 (c 0.6, CH3OH). <sup>1</sup>H NMR (CD3OD, 400 MHz): 4.39 (d, 1H, *J* 7.6 Hz, H-1), 3.96 (dd, 1H, *J*3,4 4.0 Hz, *J*4,5 2.0 Hz, H-4), 3.92 (dd, 1H, *J* 11.2 Hz, *J* 5.6 Hz, C*H*2OH), 3.86 (dd, 1H, *J*1,2 7.6 Hz, *J*2,3 6.0 Hz H-2), 3.84–3.74 (m, 3H, H-5, H-6a, H-6b), 3.67 (dd, 1H, *J* 11.2 Hz, *J* 8.4 Hz, C*H*2OH), 3.51 (s, 3H, OC*H*3), 2.32–2.26 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 125 MHz): 104.0, 76.1, 69.0, 68.3, 63.1, 59.6, 56.8, 49.0. HRMS calcd for C8H16O6-H<sup>+</sup> (M-H)+: 207.0869, found: 207.0865.

#### 3.12.2. Methyl 3-Deoxy-3-*C*-Hydroxymethyl-β-d-Galactopyranoside **1b**

Compound **1b** (TLC, DCM/MeOH, 5:1, R<sup>f</sup> 0.40) was prepared according to the general procedure *3.12* from the alcohol **14b** (46 mg, 0.10 mmol). Obtained as a white amorphous solid in 63% yield (12.6 mg, 0.06 mmol) from flash column chromatography (DCM:MeOH 12:1–6:1). [α] 25 <sup>D</sup> −32.1 (c 0.5, CH3OH). <sup>1</sup>H NMR (CD3OD, 500 MHz): 4.16 (d, 1H, *J* 7.6 Hz, H-1), 3.97 (d, 1H, *J*3,4 2.4 Hz, H-4), 3.90 (dd, 1H, *J* 10.4 Hz, *J* 4.4 Hz, C*H*2OH), 3.78 (dd, 1H, *J* 10.8 Hz, *J* 8.4 Hz, H-2), 3.72 (dd, 1H, *J* 5.6 Hz,

H-6a, H-6b), 3.55–3.51 (m, 4H, H-5, OC*H*3), 3.44 (dd, 1H, *J* 10.8 Hz, *J* 7.6 Hz, C*H*2OH), 1.73–1.66 (m, 1H, H-3). <sup>13</sup>C NMR (CD3OD, 125 MHz): 107.6, 79.8, 68.8, 67.1, 62.7, 61.2, 57.1, 49.0. HRMS calcd for C8H16O6+Na<sup>+</sup> (M+Na)+: 231.0845, found: 231.0840.
