**General process B for one-pot synthesis of thioglycoside donors containing a "NGP" group at the 2-position.**

*Step 1*. Same as *step 1* in general process A.

*Step 2*. To a mixture of phenyl disulfide (145 mg, 0.7 mmol) and NaBH4 (53 mg, 1.4 mmol) was added acetonitrile (5 mL). The mixture was stirred at rt for 30 min to 2 h until TLC indicated full conversion of the phenyl disulfide. The mixture was then added to the crude α-1,2-anhydro sugars. The reaction was stirred at rt for 5–60 min until TLC indicated full conversion of the starting material. The reaction mixture was then cooled to 0 ◦C, followed the slow addition of sodium hydride (6.0 mmol, 6 equiv, 60% oil dispersion), and allowed to stir at 0 ◦C for 10 min. After that, alkylation/acylation reagents (2–3 equiv) were added to the reaction mixture. The reaction mixture was allowed to warm to rt and then stirred for 1–4 h. Upon completion, the reaction was quenched by adding crushed ice (10 g), stirred until cessation of H2 evolution, and then extracted with ethyl acetate (3 × 80 mL). The combined organic phase was washed with water (3 × 40 mL), separated, dried with MgSO4, and evaporated in vacuo. The residue was purified by column chromatography.

**General process C for typical NIS/TfOH-promoted glycosylation procedure.** A mixture of a glycosyl donor (0.13 mmol), a glycosyl acceptor (0.10 mmol), and freshly activated molecular sieves (4 Å, 200 mg) in CH2Cl2 (1.6 mL) was stirred under an atmosphere of argon for 1 h. After NIS (0.26 mmol) and TfOH (0.013 mmol) were added at −25 ◦C, the reaction mixture was allowed to warm to rt over 1 h and then was quenched with TEA and stirred for 30 min. The mixture was then diluted with CH2Cl2, the solid was filtered-off, and the residue was washed with CH2Cl2. After the combined filtrate (30 mL) was washed with water (4 × 10 mL), the organic phase was separated, dried with MgSO4,and concentrated in vacuo. The residue was purified by silica gel flash chromatography.

*Phenyl 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-glucopyranoside (1)* [20]. Following general process A, starting from **2** (100 mg, 0.24 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **1** as a white solid (94 mg, 72%). Rf = 0.43 (petroleum ether/ethyl acetate 4:1); 1H NMR (600 MHz, chloroform-*d*) δ 7.54–7.64 (m, 2H), 7.42–7.25 (m, 16H), 7.24–7.19 (m, 2H), 4.94 (d, *J* = 11.2 Hz, 1H), 4.90–4.81 (m, 2H), 4.67–4.55 (m, 3H), 4.53 (d, *J* = 9.6 Hz, 1H), 3.83 (dd, *J* = 11.0, 2.0 Hz, 1H), 3.77 (dd, *J* = 11.0, 4.5 Hz, 1H), 3.67–3.59 (m, 2H), 3.58–3.44 (m, 2H), 2.43 (s, 1H) ppm.

*Phenyl 3*,*4-di-O-benzyl-6-O-tert-butyl-dimethylsily-1-thio-β-D-glucopyranoside (4).* Following general process A, starting from **4a** (50 mg, 0.114 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **4** as a colorless oil (40 mg, 64%). Rf = 0.41 (petroleum ether/ethyl acetate 8:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.51–7.43 (m, 2H), 7.31–7.17 (m, 13H), 4.85–4.73 (m, 3H), 4.60 (d, *J* = 10.8 Hz, 1H), 4.39 (d, *J* = 9.6 Hz, 1H), 3.86–3.74 (m, 2H), 3.57–3.45 (m, 2H), 3.41–3.32 (m, 1H), 3.28 (ddd, *J* = 9.2, 3.6, 1.8 Hz, 1H), 2.31 (d, *J* = 2.1 Hz, 1H), 0.83 (s, 9H), 0.01 (s, 6H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 138.49, 138.32, 133.03, 131.69, 128.92, 128.54, 128.47, 128.09, 128.04, 127.95, 127.84, 127.81, 87.89, 85.98, 80.44, 75.43, 75.07, 72.45, 62.14, 25.93, 18.31, −5.11, −5.34 ppm. [α] 20D <sup>=</sup> −20.3 (c 0.32, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C31H32O5S2Na+, 589.2420; found, 589.2379.

*Phenyl 3*,*4-di-O-benzyl-6-O-acetyl-1-thio-β-D-glucopyranoside (5).* Following general process A, starting from **5a** (100 mg, 0.271 mmol), after 0.5 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **5** as colorless syrup (93.6 mg, 70%). Rf = 0.58 (petroleum ether/ethyl acetate 4:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.61–7.50 (m, 2H), 7.43–7.26 (m, 13H), 4.98 (d, *J* = 11.1 Hz, 1H), 4.93–4.84 (m, 2H), 4.60 (d, *J* = 10.9 Hz, 1H), 4.52 (d, *J* = 9.7 Hz, 1H), 4.43 (dd, *J* = 11.9, 2.1 Hz, 1H), 4.23 (dd, *J* = 11.9, 5.2 Hz, 1H), 3.70–3.56 (m, 2H), 3.55–3.45 (m, 2H), 2.50 (d, *J* = 2.2 Hz, 1H), 2.08 (s, 3H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 170.67, 138.31, 137.64, 133.04, 131.59, 128.95, 128.57, 128.53, 128.24, 128.10, 128.04, 127.91, 127.00, 88.03, 85.91, 77.19, 75.41, 75.13, 72.72, 66.32, 63.18, 20.86 ppm. [α] 20D <sup>=</sup> −21.6 (c 0.25, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C28H30O6SNa+, 517.1661; found, 517.1640.

*Phenyl 3*,*4-di-O-benzyl-6-O-benzoyl-1-thio-β-D-glucopyranoside (6).* Following general process A, starting from **6a** (100 mg, 0.232 mmol), after 0.5 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **6** as a colorless oil (81.5 mg, 63%). Rf = 0.36 (petroleum ether/ethyl acetate 6:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.07–7.93 (m, 2H), 7.60 (t, *J* = 7.4 Hz, 1H), 7.54–7.05 (m, 17H), 4.96 (d, *J* = 11.0 Hz, 1H), 4.90–4.80 (m, 2H), 4.69 (dd, *J* = 12.0, 2.2 Hz, 1H), 4.61 (d, *J* = 10.8 Hz, 1H), 4.52 (d, *J* = 9.7 Hz, 1H), 4.44 (dd, *J* = 11.9, 4.7 Hz, 1H), 3.74–3.63 (m, 2H), 3.59 (t, *J* = 9.2 Hz, 1H), 3.53–3.44 (m, 1H), 2.46 (d, *J* = 2.2 Hz, 1H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 166.10, 138.25, 137.56, 133.34, 133.16, 131.07, 129.93, 129.77, 128.91, 128.60, 128.54, 128.42, 128.26, 128.16, 128.05, 127.98, 87.78, 85.93, 77.25, 77.01, 75.55, 75.25, 72.55, 63.37 ppm. [α] 20D <sup>=</sup> −31.3 (c 0.15, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C31H32O5SNa+, 579.1817; found, 579.1803.

*Phenyl 3*,*4*,*6-tri-O-benzoyl-1-thio-β-D-glucopyranoside (7).* Following general process A, starting from **7a** (100 mg, 0.218 mmol), after 20 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **7** as colorless syrup (81.6 mg, 64%). Rf = 0.43 (petroleum ether/ethyl acetate 4:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.07–7.90 (m, 6H), 7.64–7.29 (m, 12H), 7.23–7.18 (m, 2H), 5.66–5.51 (m, 2H), 4.80 (d, *J* = 9.7 Hz, 1H), 4.67 (dd, *J* = 12.2, 2.8 Hz, 1H), 4.47 (dd, *J* = 12.2, 5.8 Hz, 1H), 4.13 (ddd, *J* = 9.7, 5.7, 2.8 Hz, 1H), 3.77 (t, *J* = 9.3 Hz, 1H), 2.92–2.88 (m, 1H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 166.65, 166.06, 165.35, 133.51, 133.45, 133.41, 133.18, 129.91, 129.86, 129.82, 129.80, 129.67, 129.06, 129.01, 128.73, 128.53, 128.45, 128.41, 128.38, 88.30, 76.52, 76.20, 70.93, 68.93, 63.16 ppm. [α] 20D <sup>=</sup> −20.7 (c 0.058, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C33H28O8SNa+, 607.1367; found, 607.1403.

*Phenyl 3*,*4*,*6-tri-O-acetyl-1-thio-β-D-glucopyranoside (8).* Following general process A, starting from **8a** (100 mg, 0.367 mmol), after 15 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **8** as colorless syrup (73.2 mg, 50%). Rf = 0.44 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.59–7.53 (m, 2H), 7.39–7.28 (m, 3H), 5.13 (t, *J* = 9.3 Hz, 1H), 4.98 (t, *J* = 9.8 Hz, 1H), 4.57 (d, *J* = 9.7 Hz, 1H), 4.25–4.12 (m, 2H), 3.73 (ddd, *J* = 10.1, 5.0, 2.5 Hz, 1H), 3.50 (td, *J* = 9.4, 2.8 Hz, 1H), 2.53 (d, *J* = 2.9 Hz, 1H), 2.09 (s, 3H), 2.07 (s, 3H), 2.03 (s, 3H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 170.77, 170.61, 133.59, 130.60, 129.10, 128.72, 88.08, 75.89, 75.77, 70.31, 68.12, 62.24, 20.80, 20.76, 20.62 ppm. [α] 20D <sup>=</sup> −70.0 (c 0.05, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C31H32O5SNa+, 421.0933; found, 421.0950.

*Phenyl 3*,*4*,*6-tri-O-ethyl-1-thio-β-D-glucopyranoside (9).* Following general process A, starting from **9a** (100 mg, 0.435 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **9** as a white solid (99.7 mg, 65%): mp 83.3–84.5 ◦C; Rf = 0.31 (petroleum ether/ethyl acetate 8:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.62–7.53 (m, 2H), 7.34–7.26 (m, 3H), 4.49 (d, *J* = 9.4 Hz, 1H), 3.96–3.77 (m, 3H), 3.73 (dd, *J* = 11.0, 2.0 Hz, 1H), 3.70–3.48 (m, 4H), 4.44–4.21 (m, 4H), 2.49 (d, *J* = 2.1 Hz, 1H), 1.27–1.17 (m, 9H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 132.73, 128.88, 127.92, 88.04, 85.83, 79.64, 77.58, 72.25, 69.43, 68.73, 68.27, 66.97, 15.79, 15.72, 15.25 ppm. [α] 20D <sup>=</sup> −75.7 (c 0.14, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C31H32O5S2Na+, 379.1555; found, 379.1558.

*Phenyl 3*,*4*,*6-tri-O-tert-butyl-dimethylsily-1-thio-β-D-glucopyranoside (10).* Following general process A, starting from **10a** (100 mg, 0.205 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **10** as a colorless oil (88 mg, 70%); Rf = 0.55 (petroleum ether/ethyl acetate 50:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.56–7.49 (m, 2H), 7.32–7.19 (m, 3H), 4.59 (d, *J* = 8.9 Hz, 1H), 3.92 (dd, *J* = 11.3, 1.9 Hz, 1H), 3.74 (dd, *J* = 11.3, 5.6 Hz, 1H), 3.58–3.49 (m, 1H), 3.49–3.40 (m, 2H), 3.29 (ddd, *J* = 9.2, 5.7, 1.9 Hz, 1H), 2.17 (d, *J* = 2.7 Hz, 1H), 0.97–0.88 (m, 27H), 0.26–0.03 (m, 18H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 135.53, 130.74, 128.75, 126.78, 89.09, 81.04, 80.17, 74.40, 70.87, 62.82, 26.14, 25.96, 18.43, 18.24, −3.67, −3.85, −4.08, −4.87, −5.09, −5.33 ppm. [α] 20D <sup>=</sup> −63.8 (c 0.16, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C30H58O5Si3SNa+, 637.3210; found, 637.3174.

*Phenyl 3*,*4*,*6-tri-O-p-methoxybenzyl-1-thio-β-D-glucopyranoside (11).* Following general process A, starting from **11a** (50 mg, 0.1 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **11** as a white solid (32 mg, 52%): mp 102.3–104.6 ◦C; Rf = 0.33 (petroleum ether/ethyl acetate 6:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.60–7.54 (m, 2H), 7.36–7.23 (m, 7H), 7.18–7.08 (m, 2H), 6.93–6.79 (m, 6H), 4.83 (s, 2H), 4.76 (d, *J* = 10.4 Hz, 1H), 4.57 (d, *J* = 11.6 Hz, 1H), 4.54–4.46 (m, 3H), 3.83 (s, 9H), 3.79–3.67 (m, 2H), 3.60–3.43 (m, 4H), 2.40 (d, *J* = 2.1 Hz, 1H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 159.34, 159.32, 159.19, 132.81, 131.96, 130.66, 130.35, 130.24, 129.65, 129.37, 128.95, 128.00, 113.97, 113.82, 113.76, 88.00, 85.64, 79.47, 77.12, 74.96, 74.69, 73.09, 68.62, 55.28, 43.68, 29.71, 14.63 ppm. [α] 20D <sup>=</sup> −83.3 (c 0.09, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C31H32O5S2Na+, 655.2342; found, 655.2326.

*Phenyl 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-galactopyranoside (12).* Following general process A, starting from **12a** (50 mg, 0.12 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **12** as a white solid (34.2 mg, 53%): mp 89.8–90.4 ◦C; Rf = 0.33 (petroleum ether/ethyl acetate 4:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.59–7.48 (m, 2H), 7.41–7.07 (m, 18H), 4.89 (d, *J* = 11.5 Hz, 1H), 4.78–4.61 (m, 2H), 4.61–4.40 (m, 4H,*H*-1, ArC*H*2), 4.07–3.90 (m, 2H, H-2, *H*-4), 3.66 (s, 3H, *H*-5, *H*-6a and *H*-6b), 3.48 (dd, *J* = 9.3, 2.7 Hz, 1H, *H*-3), 2.46 (d, *J* = 2.2 Hz, 1H, O*H*) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 138.64, 137.99, 137.85, 132.60, 132.21, 128.84, 128.56, 128.46, 128.19, 127.94, 127.88, 127.85, 127.75, 127.71, 127.58, 127.47, 88.51, 83.22, 77.62, 74.41, 73.61, 73.20, 72.43, 69.07, 68.70 ppm. [α] 20D <sup>=</sup> −39.2 (c 0.13, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C31H32O5S2Na+, 565.2025; found, 565.2014.

*Phenyl 3*,*4-di-O-benzyl-6-O-tert-butyl-dimethylsily-1-thio-β-D-galactopyranoside (13).* Following general process A, starting from **13a** (50 mg, 0.114 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **13** as a colorless oil (38.6 mg, 60%). Rf = 0.45 (petroleum ether/ethyl acetate 8:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.54–7.47 (m, 2H), 7.36–7.09 (m, 13H), 4.87 (d, *J* = 11.4 Hz, 1H), 4.68 (s, 2H), 4.57 (d, *J* = 11.4 Hz, 1H), 4.48 (d, *J* = 9.6 Hz, 1H), 4.01–3.93 (m, 1H), 3.91 (d, *J* = 2.7 Hz, 1H), 3.77–3.64 (m, 2H), 3.50–3.41 (m, 2H), 2.45–2.40 (m, 1H), 0.85 (s, 9H), 0.00 (s, 6H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 138.85, 138.11, 132.67, 132.14, 128.83, 128.56, 128.16, 127.89, 127.76, 127.59, 127.52, 127.38, 88.52, 83.31, 79.31, 74.43, 73.08, 72.53, 69.10, 61.52, 25.93, 18.23, −5.32, −5.42 ppm. [α] 20D = +35.0 (c 0.1, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C32H42O5SiSNa+, 589.2420; found, 589.2396.

*Phenyl 3-O-benzyl-4-O-acetyl-6-O-tert-butyl-dimethylsily-1-thio-β-D-galactopyranoside (14).* Following general process A, starting from **14a** (50 mg, 0.127 mmol), after 0.5 h of ringopening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **14** as a white solid (34.5 mg, 52%): mp 87.1–89.3 ◦C; Rf = 0.53 (petroleum ether/ethyl acetate 4:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.55–7.48 (m, 2H), 7.32–7.21 (m, 8H), 5.56 (d, *J* = 3.0 Hz, 1H), 4.77 (d, *J* = 11.2 Hz, 1H), 4.55 (d, *J* = 9.7 Hz, 1H), 4.43 (d, *J* = 11.2 Hz, 1H), 3.73–3.65 (m, 2H), 3.64–3.54 (m, 2H), 3.46 (dd, *J* = 9.2, 3.1 Hz, 1H), 2.43 (d, *J* = 2.0 Hz, 1H), 2.04 (s, 3H), 0.84 (s, 9H), 0.00 (s, 6H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 170.05, 137.40, 132.64, 132.34, 128.87, 128.55, 128.27, 128.03, 127.82, 88.52, 80.45, 77.77, 71.73, 68.65, 65.98, 61.28, 25.81, 20.83, 18.21, −5.51, −5.61 ppm. [α] 20D <sup>=</sup> −<sup>110</sup> (c 0.03, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C27H38O6SiSNa+, 541.2056; found, 541.2047.

*Phenyl 3*,*4-di-O-benzyl-1-thio-β-D-xyloside (15).* Following general process A, starting from **15a** (50 mg, 0.169 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **15** as colorless syrup (46.3 mg, 65%). Rf = 0.53 (petroleum ether/ethyl acetate 4:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.54–7.48 (m, 2H), 7.41–7.19 (m, 13H), 4.92 (d, *J* = 5.9 Hz, 1H, *H*-1), 4.83 (d, *J* = 11.6 Hz, 1H), 4.74 (d, *J* = 11.6 Hz, 1H), 4.63 (s, 2H), 4.29 (dd, *J* = 11.7, 3.0 Hz, 1H, *H*-5b), 3.72 (q, *J* = 6.1 Hz, 1H, *H*-2), 3.63 (t, *J* = 6.1 Hz, 1H, *H*-3), 3.59–3.45 (m, 2H, *H*-4 and *H*-5a), 3.25 (d, *J* = 6.3 Hz, 1H, O*H*) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 138.08, 137.56, 134.18, 131.91, 128.98, 128.57, 128.53, 128.05, 127.89, 127.83, 127.57, 88.95, 79.32, 77.27, 75.92, 73.89, 72.41, 70.83, 63.55 ppm. [α] 20D = +85.0 (c 0.02, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C25H26O4SNa+, 445.1449; found, 445.1467.

*Phenyl 2*,*3*,*3* ,*4*,*6*,*6 -hexa-O-benzyl-D-1-thio-β-lactoside (16)* [32]. Following general process A, starting from **16a** (100 mg, 0.118 mmol), after 1 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **16** as colorless syrup (64.2 mg, 56%). Rf = 0.61 (petroleum ether/ethyl acetate 3:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.60 –7.55 (m, 2H), 7.41–7.15 (m, 33H), 5.07 (d, *J* = 11.0 Hz, 1H), 4.96 (d, *J* = 11.5 Hz, 1H), 4.85–4.73 (m, 2H), 4.73–4.62 (m, 3H), 4.58–4.47 (m, 3H), 4.48–4.37 (m, 2H), 4.34 (d, *J* = 11.7 Hz, 1H), 4.26 (d, *J* = 11.8 Hz, 1H), 3.98–3.89 (m, 2H), 3.88–3.73 (m, 3H), 3.62–3.54 (m, 1H), 3.53–3.35 (m, 6H), 2.50 (s, 1H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 139.00, 138.80, 138.71, 138.47, 132.97, 132.00, 128.87, 128.41, 128.38, 128.27, 128.23, 128.17, 128.13, 127.91, 127.87, 127.75, 127.67, 127.57, 127.49, 127.45, 127.35, 102.86, 87.40, 84.18, 82.51, 79.98, 79.76, 76.06, 75.37, 75.03, 74.67, 73.60, 73.46, 73.10, 73.02, 72.65,

71.59, 68.34, 68.14 ppm. [α] 20D <sup>=</sup> −46.3 (c 0.08, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C60H62O10SNa+, 997.3961; found, 997.3990.

*4-Methylphenyl 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-glucopyranoside (17)* [33]. Following general process A, starting from **2** (100 mg, 0.24 mmol), after 5 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **17** as a white solid (99.2 mg, 74%). Rf = 0.51 (petroleum ether/ethyl acetate 6:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.50–7.41 (m, 2H), 7.40–7.15 (m, 15H), 7.10–6.97 (m, 2H), 4.91 (d, *J* = 11.2 Hz, 1H), 4.87–4.78 (m, 2H), 4.65–4.50 (m, 3H), 4.43 (d, *J* = 9.6 Hz, 1H), 3.81–3.68 (m, 2H), 3.61–3.55 (m, 2H), 3.54–3.49 (m, 1H), 3.49–3.40 (m, 1H), 2.40 (d, *J* = 2.0 Hz, 1H), 2.31 (s, 3H) ppm.

*4-Methoxyphenyl 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-glucopyranoside (18)* [20]. Following general process A, starting from **2** (100 mg, 0.24 mmol), after 5 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **18** as colorless syrup (105 mg, 76%). Rf = 0.63 (petroleum ether/ethyl acetate 8:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.60–7.46 (m, 2H), 7.41–7.29 (m, 13H), 7.25–7.13 (m, 2H), 6.82–6.70 (m, 2H), 4.96–4.80 (m, 3H), 4.68–4.53 (m, 3H), 4.39 (d, *J* = 9.6 Hz, 1H), 3.80–3.77 (m, 5H), 3.62–3.50 (m, 3H), 3.42 (dd, *J* = 9.6, 8.4 Hz, 1H), 2.43 (s, 1H) ppm.

*4-Chlorophenyl 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-glucopyranoside (19).* Following general process A, starting from **2** (100 mg, 0.24 mmol), after 30 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **19** as colorless syrup (96 mg, 70%). Rf = 0.33 (petroleum ether/ethyl acetate 8:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.56–7.49 (m, 2H), 7.42–7.18 (m, 17H), 4.94–4.79 (m, 3H), 4.64– 4.54 (m, 3H), 4.49 (d, *J* = 9.6 Hz, 1H), 3.83–3.71 (m, 2H), 3.66–3.42 (m, 4H), 2.38 (d, *J* = 2.2 Hz, 1H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 138.38, 138.18, 137.97, 134.41, 134.32, 130.15, 129.10, 129.05, 128.81, 128.58, 128.47, 128.42, 128.00, 127.99, 127.91, 127.88, 127.70, 127.66, 87.61, 85.89, 79.35, 75.38, 75.09, 73.43, 72.44, 68.93, 38.00 ppm. [α] 20D <sup>=</sup> −<sup>115</sup> (c 0.04, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C33H33O5ClSNa+, 599.1635; found, 599.1611.

*4-Aminophenyl 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-glucopyranoside (20).* Following general process A, starting from **2** (50 mg, 0.12 mmol), after 30 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **20** as colorless syrup (45 mg, 68%). Rf = 0.35 (petroleum ether/ethyl acetate 2:1); 1H NMR (600 MHz, CDCl3) δ 7.41–7.25 (m, 15H), 7.24–7.20 (m, 2H), 6.59–6.54 (m, 2H), 4.94 (d, *J* = 11.2 Hz, 1H), 4.88–4.81 (m, 2H), 4.66–4.54 (m, 3H), 4.33 (d, *J* = 9.6 Hz, 1H), 4.15 (q, *J* = 7.1 Hz, 1H), 3.82–3.74 (m, 2H), 3.64–3.54 (m, 2H), 3.42 (t, *J* = 9.0 Hz, 1H), 2.43 (s, 1H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 147.25, 138.57, 136.38, 128.48, 128.40, 128.33, 127.98, 127.76, 127.64, 127.49, 115.33, 88.26, 85.91, 79.46, 75.26, 75.06, 73.43, 72.21, 69.04, 29.71, 29.33 ppm. [α] 20D = +61.5 (c 0.026, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C31H32O5S2Na+, 580.2130; found, 580.2120.

*Thiophen-2-ylthio 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-glucopyranoside (21).* Following general process A, starting from **2** (50 mg, 0.12 mol), after 30 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **21** as a red solid (41 mg, 63%): mp 90.9–92.1 ◦C; Rf = 0.52 (petroleum ether/ethyl acetate 5:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.47–7.09 (m, 17H), 6.98 (dd, *J* = 5.5, 3.5 Hz, 1H), 4.92–4.76 (m, 3H), 4.70–4.51 (m, 3H), 4.30 (d, *J* = 9.4 Hz, 1H), 3.82–3.70 (m, 2H), 3.62–3.46 (m, 3H), 3.42 (ddd, *J* = 9.0, 6.2, 2.7 Hz, 1H), 2.36 (d, *J* = 2.4 Hz, 1H) ppm. 13C NMR (100 MHz, chloroform*d*) δ 138.39, 138.04, 136.17, 131.08, 128.56, 128.43, 128.34, 128.00, 127.96, 127.88, 127.81, 127.63, 127.53, 87.53, 85.80, 79.69, 75.39, 75.06, 73.50, 71.86, 68.87, 29.39 ppm. [α] 20D <sup>=</sup> −46.6 (c 0.058, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C31H32O5S2Na+, 571.1589; found, 571.1602.

*Benzothiazol-2-yl 3*,*4*,*6-tri-O-benzyl-1-thio-β-D-glucopyranoside (22).* Following general process A, starting from **2** (50 mg, 0.12 mmol), after 30 min of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **22** as a white solid (51.3 mg, 72%): mp 119.9–123.0 ◦C; Rf = 0.36 (petroleum ether/ethyl

acetate 6:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.94 (d, *J* = 8.1 Hz, 1H), 7.72 (d, *J* = 8.0 Hz, 1H), 7.45 (t, *J* = 7.7 Hz, 1H), 7.39–7.23 (m, 14H), 7.23–7.17 (m, 2H), 5.07 (d, *J* = 9.5 Hz, 1H), 4.99–4.80 (m, 3H), 4.67–4.47 (m, 3H), 3.86–3.63 (m, 6H), 3.13 (d, *J* = 3.1 Hz, 1H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 211.54, 152.68, 138.40, 138.11, 138.00, 128.56, 128.45, 128.36, 128.01, 127.95, 127.89, 127.85, 127.76, 127.61, 126.31, 125.06, 122.43, 121.02, 86.49, 85.95, 79.94, 75.49, 75.10, 73.50, 68.65, 29.34, 14.14 ppm. [α] 20D <sup>=</sup> −64.3 (c 0.07, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]<sup>+</sup> calculated for C34H33NO5S2Na+, 622.1698; found, 622.1707.

*Phenyl 3*,*4*,*6-tri-O-benzyl-1-seleno-β-D-glucopyranoside (26)* [34]. Following general process A, starting from **2** (100 mg, 0.24 mmol), after 12 h of ring-opening reaction for the crude anhydro sugar, purification by silica gel flash column chromatography afforded **26** as a white solid (85.5 mg, 61%). Rf = 0.43 (petroleum ether/ethyl acetate 8:1); 1H NMR (400 MHz, chloroform-*d*) δ 7.72–7.66 (m, 2H), 7.41–7.19 (m, 18H), 4.93 (d, *J* = 11.2 Hz, 1H), 4.89–4.82 (m, 2H), 4.75 (d, *J* = 9.7 Hz, 1H), 4.67–4.54 (m, 3H), 3.85–3.74 (m, 2H), 3.67–3.57 (m, 2H), 3.56–3.47 (m, 2H) ppm.

*Phenyl 3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-1-thio-glucopyranoside (28).* Following the general process B, starting from **2** (100 mg, 0.24 mmol), after 2 h of ring-opening reaction for the crude anhydro sugar and then reaction with PicBr•HBr (2.0 equiv) for 1 h in the presence of sodium hydride (6 equiv), the residue was purified by column chromatography on silica gel (ethyl acetate-hexane gradient elution) to afford **28** as a colorless syrup (101 mg, 66%). Rf = 0.33 (petroleum ether/ethyl acetate 4:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.58–8.50 (m, 1H), 7.65 (td, *J* = 7.7, 1.9 Hz, 1H), 7.58–7.49 (m, 3H), 7.40–7.09 (m, 19H), 5.04 (d, *J* = 12.4 Hz, 1H), 4.96–4.75 (m, 4H), 4.69 (d, *J* = 9.6 Hz, 1H), 4.64–4.49 (m, 3H), 3.84–3.69 (m, 3H), 3.65 (t, *J* = 9.3 Hz, 1H), 3.55 (t, *J* = 9.1 Hz, 2H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 158.30, 149.00, 138.29, 138.20, 138.06, 136.52, 133.54, 132.04, 128.90, 128.44, 128.41, 128.35, 128.00, 127.92, 127.82, 127.70, 127.65, 127.56, 127.50, 122.35, 121.65, 87.19, 86.55, 81.32, 79.13, 75.93, 75.81, 75.06, 73.43, 69.04 ppm. [α] 20D <sup>=</sup> −45 (c 0.04, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C39H39O5NSNa+, 656.2447; found, 656.2416.

*Phenyl 3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-1-thio-galactopyranoside (29).* Following the general process B, starting from **12a** (100 mg, 0.24 mmol), after 2 h of ring-opening reaction for the crude anhydro sugar, and then reaction with PicBr•HBr (2.0 equiv) for 1 h in the presence of sodium hydride (6 equiv), the residue was purified by column chromatography on silica gel (ethyl acetate-hexane gradient elution) to afford **29** as a colorless syrup (73 mg, 48%). Rf = 0.35 (petroleum ether/ethyl acetate 4:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.53 (d, *J* = 5.0 Hz, 1H), 7.62 (t, *J* = 7.6 Hz, 1H), 7.56–7.43 (m, 3H), 7.41–7.09 (m, 19H), 4.98–4.87 (m, 3H), 4.75–4.63 (m, 3H), 4.58 (d, *J* = 11.5 Hz, 1H), 4.51–4.37 (m, 2H), 4.01–3.90 (m, 2H), 3.72–3.57 (m, 4H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 158.67, 148.91, 138.75, 138.14, 137.89, 136.40, 133.94, 131.56, 128.80, 128.46, 128.39, 128.22, 127.96, 127.86, 127.84, 127.64, 127.49, 127.11, 122.24, 121.79, 87.52, 83.91, 78.04, 77.40, 77.34, 77.08, 76.76, 76.28, 74.49, 73.62, 73.48, 72.57, 68.79 ppm. [α] 20D = +9.1 (c 0.33, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C39H39O5NSNa+, 656.2447; found, 656.2433.

*Phenyl 3*,*4*,*6-Tri-O-benzyl-2-O-(phenylmethoxy)methyl-β-D-1-thio-glucopyranoside (30)* [21]. Following the general process B, starting from **2** (100 mg, 0.24 mmol), after 2 h of ringopening reaction for the crude anhydro sugar and then reaction with BOMCl (2.0 equiv) for 3 h in the presence of sodium hydride (6 equiv), the residue was purified by column chromatography on silica gel (ethyl acetate-hexane gradient elution) to afford **30** as a white solid (100.3 mg, 63%). Rf = 0.53 (petroleum ether/ethyl acetate 6:1); 1H NMR (400 MHz, CDCl3) δ 7.59–7.49 (m, 2H), 7.39–7.12 (m, 23H), 5.06 (d, *J* = 6.4 Hz, 1H), 4.94 (d, *J* = 6.4 Hz, 1H), 4.92 –4.83 (m, 3H), 4.79 (d, *J* = 10.8 Hz, 1H), 4.69–4.58 (m, 3H), 4.58–4.49 (m, 2H), 3.77 (dd, *J* = 10.9, 2.0 Hz, 1H), 3.74–3.61 (m, 4H), 3.52 (m, 1H) ppm.

*Phenyl 3*,*4*,*6-Tri-O-benzyl-2-O-(cyanomethyl)-β-D-1-thio-glucopyranoside (31)* [18]. Following the general process B, starting from **2** (100 mg, 0.24 mmol), after 2 h of ring-opening reaction for the crude anhydro sugar and then reaction with bromoacetonitrile (2.5 equiv) for 2 h in the presence of sodium hydride (6 equiv), the residue was purified by column chromatography on silica gel (ethyl acetate-hexane gradient elution) to afford **31** as a white

solid (76.8 mg, 55%). Rf = 0.53 (petroleum ether/ethyl acetate 6:1); 1H NMR (400 MHz, CDCl3) δ 7.61–7.52 (m, 2H), 7.41–7.22 (m, 16H), 7.19 (dd, *J* = 7.2, 2.3 Hz, 2H), 4.90–4.82 (m, 2H), 4.80 (d, *J* = 10.9 Hz, 1H), 4.64–4.56 (m, 2H), 4.55 (s, 1H), 4.52 (t, *J* = 1.8 Hz, 1H), 4.51–4.39 (m, 2H), 3.77 (dd, *J* = 10.9, 2.1 Hz, 1H), 3.72 (dd, *J* = 10.9, 4.3 Hz, 1H), 3.67–3.62 (m, 2H), 3.47 (m, 1H), 3.35 (m, 1H) ppm.

*Phenyl 3*,*4*,*6-Tri-O-benzyl-2-O-(2-cyanobenzyl)-β-D-1-thio-glucopyranoside (32)* [22]. Following the general process B, starting from **2** (100 mg, 0.24 mmol), after 2 h of ring-opening reaction for the crude anhydro sugar and then reaction with 2-cyanobenzyl bromide (2.0 equiv) for 1 h in the presence of sodium hydride (6 equiv), the residue was purified by column chromatography on silica gel (ethyl acetate-hexane gradient elution) to afford **32** as a colorless oil (107.4 mg, 68%). Rf = 0.31 (petroleum ether/ethyl acetate 6:1); 1H NMR (400 MHz, CDCl3) δ 7.73–7.53 (m, 6H), 7.43–7.19 (m, 18H), 5.11 (d, *J* = 12.5 Hz, 1H), 5.03 (d, *J* = 12.5 Hz, 1H), 4.91–4.79 (m, 3H), 4.73–4.56 (m, 4H), 3.83 (dd, *J* = 10.9, 2.0 Hz, 1H), 3.78 (d, *J* = 4.4 Hz, 1H), 3.77–3.66 (m, 2H), 3.60–3.51 (m, 2H) ppm.

*Phenyl 3*,*4*,*6-Tri-O-benzyl-2-O-benzoyl-β-D-1-thio-glucopyranoside (33)* [35]. Following the general process B, starting from **2** (100 mg, 0.24 mmol), after 2 h of ring-opening reaction for the crude anhydro sugar and then reaction with BzCl (3.0 equiv) for 2 h in the presence of sodium hydride (6 equiv), the residue was purified by column chromatography on silica gel (ethyl acetate-hexane gradient elution) to afford **33** as a white solid (97.8 mg, 63%). Rf = 0.61 (petroleum ether/ethyl acetate 6:1); 1H NMR (400 MHz, CDCl3) δ 8.11–8.03 (m, 2H), 7.60 (d, *J* = 7.4 Hz, 1H), 7.54–7.44 (m, 4H), 7.43–7.20 (m, 13H), 7.18–7.11 (m, 5H), 5.31 (dd, *J* = 10.0, 9.0 Hz, 1H), 4.87–4.78 (m, 2H), 4.75 (d, *J* = 11.0 Hz, 1H), 4.70–4.55 (m, 4H), 3.91–3.82 (m, 2H), 3.81–3.74 (m, 2H), 3.64 (m, 1H) ppm.

*Phenyl 3*,*4*,*6-Tri-O-benzyl-2-O-pivaloyl-β-D-1-thio-glucopyranoside (34)* [36]. Following the general process B, starting from **2** (100 mg, 0.24 mmol), after 2 h of ring-opening reaction for the crude anhydro sugar and then reaction with PivCl (3.0 equiv) for 2 h in the presence of sodium hydride (6 equiv), the residue was purified by column chromatography on silica gel (ethyl acetate-hexane gradient elution) to afford **34** as a white solid (78.3 mg, 52%). Rf = 0.73 (petroleum ether/ethyl acetate 8:1); 1H NMR (400 MHz, CDCl3) δ 7.58–7.49 (m, 2H), 7.41–7.22 (m, 16H), 7.19 (dd, *J* = 7.2, 2.4 Hz, 2H), 5.13 (t, 1H), 4.84–4.76 (m, 2H), 4.75–4.53 (m, 5H), 3.81 (dd, 1 H, J = 1.5, 11.0 Hz, 1H), 3.79–3.67 (m, 3H), 3.59 (m, 1H), 1.26 (s, 9H) ppm.

*Methyl 2*,*3*,*4-tri-O-benzoyl-6-O-(3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-α-Dglucopyranoside (35).* Following the general process C, the glycosylation between **28** (100 mg, 0.16 mmol, 1.3 equiv) and methyl 2,3,4-tri-*O*-benzoyl-α-D-glucopyranoside (1.0 equiv) led to **30**. Purification by silica gel flash column chromatography afforded **35** as a colorless syrup (87.5 mg, 70%, β-only). Rf = 0.26 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.53 (d, *J* = 4.9 Hz, 1H), 8.03–7.76 (m, 7H), 7.66–7.58 (m, 1H), 7.55–7.46 (m, 3H), 7.45–7.20 (m, 19H), 7.17–7.07 (m, 3H), 6.14 (t, *J* = 9.8 Hz, 1H), 5.42 (t, *J* = 9.9 Hz, 1H), 5.24–5.16 (m, 2H), 5.11 (d, *J* = 3.6 Hz, 1H), 4.95–4.83 (m, 2H), 4.82–4.73 (m, 2H), 4.56–4.46 (m, 3H), 4.44 (d, *J* = 12.3 Hz, 1H), 4.34 (td, *J* = 8.7, 8.2, 4.1 Hz, 1H), 4.10 (dd, *J* = 10.9, 2.1 Hz, 1H), 3.77 (dd, *J* = 11.1, 7.8 Hz, 1H), 3.73–3.57 (m, 4H), 3.53–3.41 (m, 2H), 3.34 (s, 3H) ppm. 13C NMR (100 MHz, chloroform-*d*) δ 165.81, 165.74, 165.50, 158.78, 148.95, 138.50, 138.14, 138.09, 136.46, 133.42, 133.33, 133.05, 129.93, 129.90, 129.66, 129.28, 129.11, 128.90, 128.41, 128.34, 128.25, 127.98, 127.94, 127.75, 127.58, 122.18, 121.45, 103.94, 96.68, 84.47, 82.78, 77.65, 75.68, 75.40, 75.00, 74.95, 73.45, 72.11, 70.49, 69.91, 68.97, 68.61, 55.52 ppm. [α] 20D = +40.9 (c 0.22, CH2Cl2); HRMS (ESI-TOF) (*m/z*): [M + Na]+ calculated for C61H59O14NNa+, 1052.3833 ; found, 1052.3814.

*Methyl 2*,*3*,*4-tri-O-benzyl-6-O-(3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-α-Dglucopyranoside (36)* [37]. Following the general process C, the glycosylation between **28** (100 mg, 0.16 mmol, 1.3 equiv) and methyl 2,3,4-tri-*O*-benzyl-α-D-glucopyranoside (1.0 equiv) led to **36**. Purification by silica gel flash column chromatography afforded **36** as a colorless syrup (97.7 mg, 82%, β-only). Rf = 0.46 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.44 (d, *J* = 4.8 Hz, 1H), 7.48–7.20 (m, 28H), 7.19–7.11 (m,

4H), 7.02 (t, *J* = 6.1 Hz, 1H), 5.13 (d, *J* = 12.9 Hz, 1H), 4.96–4.85 (m, 3H), 4.84–4.70 (m, 4H), 4.68–4.59 (m, 2H), 4.58–4.51 (m, 4H), 4.47 (d, *J* = 11.0 Hz, 1H), 4.39 (d, *J* = 7.8 Hz, 1H), 4.17 (d, *J* = 10.7 Hz, 1H), 3.95 (t, *J* = 9.3 Hz, 1H), 3.78 (dt, *J* = 14.3, 7.1 Hz, 1H), 3.72–3.61 (m, 4H), 3.60–3.40 (m, 5H), 3.31 (s, 3H) ppm.

*Methyl 2*,*3*,*6-tri-O-benzyl-4-O-(3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-α-Dglucopyranoside (37)* [37]. Following the general process C, the glycosylation between **28** (100 mg, 0.16 mmol, 1.3 equiv) and methyl 2,3,6-tri-*O*-benzyl-α-D-glucopyranoside (1.0 equiv) led to **37**. Purification by silica gel flash column chromatography afforded **37** as a colorless syrup (59.6 mg, 50%, β-only). Rf = 0.48 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.50 (d, *J* = 4.8 Hz, 1H), 7.54 (t, *J* = 7.7 Hz, 1H), 7.45–7.06 (m, 32H), 5.07 (d, *J* = 11.3 Hz, 1H), 4.96 (d, *J* = 13.5 Hz, 1H), 4.90–4.71 (m, 6H), 4.64–4.52 (m, 4H), 4.48–4.34 (m, 4H), 3.96 (t, *J* = 9.5 Hz, 1H), 3.87–3.77 (m, 2H), 3.72 (d, *J* = 10.9 Hz, 1H), 3.65–3.57 (m, 2H), 3.48 (m, 5H), 3.34 (s, 3H), 3.31–3.27 (m, 1H) ppm.

*Methyl 2*,*4*,*6-tri-O-benzyl-3-O-(3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-α-Dglucopyranoside (38)* [37]. Following the general process C, the glycosylation between **28** (100 mg, 0.16 mmol, 1.3 equiv) and methyl 2,4,6-tri-*O*-benzyl-α-D-glucopyranoside (1.0 equiv) led to **38**. Purification by silica gel flash column chromatography afforded **38** as a colorless syrup (95.4 mg, 80%, β-only). Rf = 0.65 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.56 (d, *J* = 4.9 Hz, 1H), 7.56–7.47 (m, 2H), 7.40–7.04 (m, 31H), 5.29 (d, *J* = 13.5 Hz, 1H), 5.14–4.95 (m, 4H), 4.89 (d, *J* = 10.9 Hz, 1H), 4.83 (d, *J* = 10.6 Hz, 1H), 4.70–4.53 (m, 3H), 4.53–4.33 (m, 7H), 3.81–3.64 (m, 6H), 3.63–3.48 (m, 4H), 3.45 (d, *J* = 9.4 Hz, 1H), 3.30 (s, 3H) ppm.

*Methyl 3*,*4*,*6-tri-O-benzyl-2-O-(3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-α-Dglucopyranoside (39)* [37]. Following the general process C, the glycosylation between **28** (100 mg, 0.16 mmol, 1.3 equiv) and methyl 3,4,6-tri-*O*-benzyl-α-D-glucopyranoside led to **39**. Purification by silica gel flash column chromatography afforded **39** as a colorless syrup (91.8 mg, 77%, β-only). Rf = 0.55 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.42 (d, *J* = 5.0 Hz, 1H), 7.45–7.10 (m, 30H), 7.11–6.96 (m, 3H), 5.18 (d, *J* = 13.4 Hz, 1H), 5.03–4.85 (m, 3H), 4.85–4.70 (m, 4H), 4.67–4.56 (m, 3H), 4.55–4.40 (m, 4H), 4.01 (t, *J* = 9.2 Hz, 1H), 3.89–3.61 (m, 10H), 3.58 (t, *J* = 7.4 Hz, 1H), 3.43 (m, 1H), 3.39 (s, 3H) ppm.

*1*,*2:5*,*6-Di-O-isopropylidine-3-O-(3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-α-Dglucofuranose (40)* [37]. Following the general process C, the glycosylation between **28** (100 mg, 0.16 mmol, 1.3 equiv) and 1,2:5,6-bis-*O*-(1-methylethylidene)-α-D-glucofuranose (1.0 equiv) led to **40**. Purification by silica gel flash column chromatography afforded **40** as colorless syrup (49.2 mg, 52%, β-only). Rf = 0.35 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.56 (d, *J* = 4.9 Hz, 1H), 7.67–7.56 (m, 1H), 7.43–7.22 (m, 14H), 7.21–7.08 (m, 3H), 5.81 (d, *J* = 3.7 Hz, 1H), 4.93–4.86 (m, 2H), 4.85–4.75 (m, 3H), 4.66–4.47 (m, 5H), 4.43 (q, *J* = 5.9 Hz, 1H), 4.38–4.28 (m, 2H), 4.12–4.01 (m, 2H), 3.78–3.58 (m, 4H), 3.47–3.38 (m, 2H), 1.48 (s, 3H), 1.41 (s, 3H), 1.31 (s, 3H), 1.25 (s, 3H) ppm.

*Methyl 2*,*3*,*4-tri-O-benzyl-6-O-(3*,*4*,*6-tri-O-benzyl-2-O-picolyl-β-D-galactopyranosyl)-α-Dglucopyranoside (41)* [37]. Following the general process C, the glycosylation between **29** (100 mg, 0.16 mmol, 1.3 equiv) and methyl 2,3,4-tri-*O*-benzyl-α-D-glucopyranoside (1.0 equiv) led to **41**. Purification by silica gel flash column chromatography afforded **41** as a colorless syrup (102.5 mg, 86%, β-only). Rf = 0.36 (petroleum ether/ethyl acetate 2:1); 1H NMR (400 MHz, chloroform-*d*) δ 8.43 (d, *J* = 4.8 Hz, 1H), 7.48–7.39 (m, 2H), 7.39–7.08 (m, 30H), 7.04 (q, *J* = 4.7 Hz, 1H), 5.09 (d, *J* = 13.2 Hz, 1H), 4.98–4.87 (m, 3H), 4.80–4.38 (m, 11H), 4.35 (d, *J* = 7.7 Hz, 1H), 4.13 (d, *J* = 10.8 Hz, 1H), 3.97–3.84 (m, 3H), 3.79 (dd, *J* = 10.5, 5.0 Hz, 1H), 3.52 (m, 7H), 3.28 (s, 3H) ppm.

**Supplementary Materials:** The following supporting information can be downloaded at: https: //www.mdpi.com/article/10.3390/molecules27185980/s1, Experimental methods, synthesis of thiocontaining glycosides, Characterization of unknown compounds, 1H NMR and 13C NMR spectra, references [38–46].

**Author Contributions:** Conceptualization, Y.-F.G., T.L. and H.D.; methodology, Y.-F.G. and T.L.; validation, Y.-F.G. and T.L.; formal analysis, G.-J.F. and C.-Y.L.; data curation, G.-J.F. and C.-Y.L.; writing—original draft preparation, Y.-F.G., T.L. and H.D.; writing—review and editing, Y.-F.G. and H.D.; supervision, H.D. project administration, H.D.; funding acquisition, H.D. All authors have read and agreed to the published version of the manuscript.

**Funding:** This research was founded by the National Nature Science Foundation of China (Nos. 21772049).

**Institutional Review Board Statement:** Not applicable.

**Informed Consent Statement:** Not applicable.

**Data Availability Statement:** Not applicable.

**Acknowledgments:** The authors aregrateful to the staffs in the Analytical and Test Center of HUST for support with the NMR instruments.

**Conflicts of Interest:** The authors declare no conflict of interest.

**Sample Availability:** Samples of the compounds are available from the authors.
