*3.2. Synthesis*

3.2.1. General Procedure for Synthesis of Acetylated Thioglycosides **13a–d–16a**–**d**

2-Chloro(bromo)-3-methoxyquinone, **5**, **6**, **11**, and **12** (0.50 mM), and per-*O*-acetylated 1-mercaptosugar derivatives **2a**–**d** (0.55 mM) were dissolved in acetone (30 mL) and 76 mg (0.55 mM) of dry finely powdered K2CO3 was added. The resulting mixture was stirred for 2 h at room temperature until the consumption of thioglicose and conversion of starting quinone. Precipitate of inorganic salt was filtered, the filtrate was dried in a vacuum, and the residue was subjected to preparative TLC (system B for **13a**–**d** and system A for others). The main fraction was washed off from silica gel with acetone, dried, and recrystallized from MeOH to give pure thioglycoside **13a**–**d**–**16a**–**d**.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d-*glucopyranosyl-1-thio)-3,5,8-trimethoxy-1,4-naphthoquinone* (**13a**); yield 276 mg (90%), orange solid, *Rf* 0.37 (B), m.p. 162–165 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 1.97 (s, 3H, COCH3), 2.00 (s, 3H, COCH3), 2.01 (s, 3H, COCH3), 2.06 (s, 3H, COCH3), 3.70 (m, 1H, H-5- ), 3.93 (s, 3H, -OCH3), 3.94 (s, 3H, -OCH3), 3.99 (dd, 1H, *J* = 12.4, 1.9 Hz, H-6- a), 4.14 (s, 3H, -OCH3), 4.20 (dd, 1H, *J* = 12.4, 4.5, Hz, H-6- b), 5.10 (t, 1H, *J* = 9.6 Hz, H-2- ), 5.12 (t, 1H, *J* = 9.7 Hz, H-4- ), 5.26 (t, 1H, *J* = 9.2 Hz, H-3- ), 5.61 (d, 1H, *J* = 10.1 Hz, H-1- ), 7.23 (d, 1H, *J* = 9.5 Hz, Ar-H), 7.27 (d, 1H, *J* = 9.5 Hz, Ar-H). 13C-NMR(125 MHz, CDCl3), <sup>δ</sup>: 20.6 (3 <sup>×</sup> COCH3), 20.7 (COCH3), 56.9 (-OCH3), 57.1 (-OCH3), 61.1 (-OCH3), 61.8 (C-6- ), 68.2 (C-4- ), 71.2 (C-2- ), 74.1 (C-3- ), 75.7 (C-5- ), 80.7 (C-1- ), 119.4, 120.5, 120.7, 122.2, 126.9 (C-2), 153.0, 153.7, 158.3 (C-3), 169.3 (COCH3), 169.4 (COCH3), 170.2 (COCH3), 170.6 (COCH3), 178.0, 181.4. IR (CHCl3): 3050, 2943, 2842, 1755, 1663, 1597, 1571, 1479, 1463, 1435, 1413, 1368, 1334, 1270, 1243, 1210, 1193 cm<sup>−</sup>1. HRMS (ESI): *<sup>m</sup>*/*<sup>z</sup>* [M <sup>−</sup> H]<sup>−</sup> calcd. for C27H29O14S 609.1284, found 609.1281.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d-*galactopyranosyl-1-thio)-3,5,8-trimethoxy-1,4-naphthoquinone* (**13b**); yield 253 mg (82.5%), orange solid, *Rf* 0.37 (B), m.p. 99–101 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 1.94 (s, 3H, COCH3), 1.98 (s, 3H, COCH3), 2.08 (s, 3H, COCH3), 2.13 (s, 3H, COCH3), 3.91 (m, 1H, H-5- ), 3.93 (s, 3H, -OCH3), 3.95 (s, 3H, -OCH3), 4.02 (m, 2H, H-6- a, H-6- b), 4.14 (s, 3H, -OCH3), 5.10 (dd, 1H, *J* = 9.9, 3.5 Hz, H-3- ), 5.31 (t, 1H, *J* = 10.0 Hz, H-2- ), 5.42 (m, 1H, H-4- ), 5.59 (d, 1H, *J* = 10.2 Hz, H-1- ), 7.23 (d, 1H, *J* = 9.5 Hz, Ar-H), 7.27 (d, 1H, *J* = 9.5 Hz, Ar-H). 13C-NMR(125 MHz, CDCl3), δ: 20.5 (COCH3), 20.6 (2 × COCH3), 20.8 (COCH3), 56.9 (-OCH3), 57.0 (-OCH3), 61.0 (C-6- ), 61.1 (-OCH3), 67.2 (C-4- ), 68.4 (C-2- ), 72.0 (C-3- ), 74.3 (C-5- ), 81.5 (C-1- ), 119.4, 120.5, 120.6, 122.1, 126.9 (C-2), 153.1, 153.7, 158.5 (C-3), 169.6 (COCH3), 170.0 (2 × COCH3), 170.2 (COCH3), 178.1, 181.3. IR (CHCl3): 3054, 3006, 2941, 2842, 1750, 1663, 1597, 1571, 1479, 1463, 1435, 1413, 1372, 1334, 1270, 1251, 1185, 1155, 1085, 1060, 1022 cm<sup>−</sup>1. HRMS (ESI): *<sup>m</sup>*/*<sup>z</sup>* [M <sup>−</sup> H]<sup>−</sup> calcd. for C27H29O14S 609.1284, found 609.1283.

*2-(2,3,4-Tri-O-acetyl-*β*-*d-*xylopyranosyl-1-thio)-3,5,8-trimethoxy-1,4-naphthoquinone* (**13c**); yield 230 mg (85%), orange solid, *Rf* 0.39 (B), m.p. 197–199 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 2.04 (s, 3H, COCH3), 2.06 (s, 3H, COCH3), 2.08 (s, 3H, COCH3), 3.39 (dd, 1H, *J* = 11.9, 8.3 Hz, H-5- a), 3.93 (s, 3H, -OCH3), 3.95 (s, 3H, -OCH3), 4.15 (s, 3H, -OCH3), 4.21 (dd, 1H, *J* = 11.9, 4.7 Hz, H-5- b), 4.94 (m, 1H, H-4- ), 5.04 (t, 1H, *J* = 8.0 Hz, H-2- ), 5.20 (t, 1H, *J* = 8.0 Hz, H-3- ), 5.60 (d, 1H, *J* = 8.0 Hz, H-1- ), 7.24 (d, 1H, *J* = 9.5 Hz, Ar-H), 7.27 (d, 1H, *J* = 9.5 Hz, Ar-H). 13C-NMR(125 MHz, CDCl3), <sup>δ</sup>: 20.7 (3 <sup>×</sup> COCH3), 56.9 (-OCH3), 57.1 (-OCH3), 61.2 (-OCH3), 64.9 (C-5- ), 68.6 (C-4- ), 70.6 (C-2- ), 71.7 (C-3- ), 81.6 (C-1- ), 119.4, 120.6, 120.8, 122.0, 126.6 (C-2), 153.3, 153.8, 159.4 (C-3), 169.4 (COCH3), 169.7 (COCH3), 169.8 (COCH3), 178.3, 181.3. IR (CDCl3): 3054, 3018, 3006, 2942, 2842, 1752, 1663, 1597, 1571, 1478, 1463, 1435, 1413, 1371, 1334, 1272, 1248, 1210, 1185, 1062, 1024 cm<sup>−</sup>1. HRMS (ESI): *m*/*z* [M <sup>−</sup> H]<sup>−</sup> calcd. for C24H25O12S 537.1072, found 537.1073.

*2-(2,3,4-Tri-O-acetyl-*α*-*l-*arabinopyranosyl-1-thio)-3,5,8-trimethoxy-1,4-naphthoquinone* (**13d**); yield 236 mg (87.2%), dark orange solid, *Rf* 0.39 (B), m.p. 92–94 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 2.07 (s, 3H, COCH3), 2.10 (s, 3H, COCH3), 2.11 (s, 3H, COCH3), 3.64 (dd, 1H, *J* = 12.6, 2.3 Hz, H-5- a), 3.92 (s, 3H, -OCH3), 3.94 (s, 3H, -OCH3), 4.08 (dd, 1H, *J* = 12.6, 4.3 Hz, H-5- b), 4.15 (s, 3H, -OCH3), 5.14 (dd, 1H, *J* = 8.2, 3.4 Hz, H-3- ), 5.27 (m, 1H, H-4- ), 5.31 (t, 1H, *J* = 7.9 Hz, H-2- ), 5.60 (d, 1H, *J* = 7.9 Hz, H-1- ), 7.23 (d, 1H, *J* = 9.5 Hz, Ar-H), 7.26 (d, 1H, *J* = 9.5 Hz, Ar-H). 13C-NMR(125 MHz, CDCl3), δ: 20.7 (COCH3), 20.8 (COCH3), 20.9 (COCH3), 56.9 (-OCH3), 57.2 (-OCH3), 61.2 (-OCH3), 65.3 (C-5- ), 67.6 (C-4- ), 69.2 (C-2- ), 70.3 (C-3- ), 81.8 (C-1- ), 119.4, 120.6, 120.7, 122.1, 127.1 (C-2), 153.2, 153.7, 159.1 (C-3), 169.5 (COCH3), 169.8 (COCH3), 170.2 (COCH3), 178.3, 181.4. IR (CHCl3): 3054, 3005, 2941, 2841, 1747, 1661, 1597, 1570, 1478, 1463, 1435, 1412, 1372, 1335, 1272, 1250, 1185, 1159, 1105, 1087, 1060, 1022 cm<sup>−</sup>1. HRMS (ESI): *m*/*z* [M − H]<sup>−</sup> calcd. for C24H25O12S 537.1072, found 537.1070.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d-*glucopyranosyl-1-thio)-6,7-dichloro-3,5,8-trimethoxy-1,4-naphthoquinone* (**14a**); yield 279 mg (82%), yellow solid, *Rf* 0.48 (A), m.p. 103–105 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 1.96 (s, 3H, COCH3), 2.01 (s, 3H, COCH3), 2.02 (s, 3H, COCH3), 2.08 (s, 3H, COCH3), 3.67 (m, 1H, H-5- ), 3.98 (s, 6H, 2 × -OCH3), 4.01 (dd, 1H, *J* = 12.6, 2.2 Hz, H-6- a), 4.15 (s, 3H, -OCH3), 4.18 (dd, 1H, *J* = 12.6, 4.7 Hz, H-6- b), 5.10 (m, 2H, H-2- , H-4- ), 5.27 (t, 1H, *J* = 9.3 Hz, H-3- ), 5.60 (d, 1H, *J* = 10.2 Hz, H-1- ). 13C-NMR(125 MHz, CDCl3), <sup>δ</sup>: 20.5 (2 <sup>×</sup> COCH3), 20.6 (2 <sup>×</sup> COCH3), 61.3 (-OCH3), 61.8 (C-6- ), 62.3 (-OCH3), 62.4 (-OCH3), 68.1 (C-4- ), 71.1 (C-2- ), 74.0 (C-3- ), 76.0 (C-5- ), 80.4 (C-1- ), 124.1, 125.7, 127.6 (C-2), 136.2, 136.9, 152.6, 153.0, 158.3 (C-3), 169.3 (COCH3), 169.4 (COCH3), 170.1 (COCH3), 170.5 (COCH3), 176.4, 179.7. IR (CHCl3): 3050, 2944, 2857, 1756, 1670, 1581, 1547, 1459, 1440, 1380, 1326, 1304, 1241, 1207, 1194, 1030 cm−1. HRMS (ESI): *m*/*z* [M <sup>−</sup> H]<sup>−</sup> calcd. for C27H27Cl2O14S 677.0504, found 677.0504.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d-*galactopyranosyl-1-thio)-6,7-dichloro-3,5,8-trimethoxy-1,4-naphthoquinone* (**14b**); yield 302 mg (88.8%), orange solid, *Rf* 0.48 (A), m.p. 80–81 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 1.95 (s, 3H, COCH3), 1.99 (s, 3H, COCH3), 2.09 (s, 3H, COCH3), 2.14 (s, 3H, COCH3), 3.90 (m, 1H, H-5- ), 3.98 (s, 6H, 2 × -OCH3), 4.03 (m, 2H, H-6- a, H-6- b), 4.16 (s, 3H, -OCH3), 5.11 (dd, 1H, *J* = 9.9, 3.5 Hz, H-3- ), 5.30 (t, 1H, *J* = 10.0 Hz, H-2- ), 5.42 (m, 1H, H-4- ), 5.57 (d, 1H, *J* = 10.2 Hz, H-1- ). 13C-NMR(125 MHz, CDCl3), <sup>δ</sup>: 20.5 (2 <sup>×</sup> COCH3), 20.6(COCH3), 20.7 (COCH3), 61.2 (C-6- ), 61.7 (-OCH3), 62.3 (-OCH3), 62.4 (-OCH3), 67.2 (C-4- ), 68.3 (C-2- ), 71.9 (C-3- ), 74.6 (C-5- ), 81.3 (C-1- ), 124.1, 125.6, 127.7 (C-2), 136.2, 136.9, 152.7, 153.0, 158.4 (C-3), 169.6 (COCH3), 170.0 (COCH3), 170.2 (COCH3), 170.3 (COCH3), 176.5, 179.7. IR (CHCl3): 3053, 3007, 2944, 2856, 1751, 1670, 1580, 1459, 1440, 1380, 1326, 1304, 1245, 1191, 1113, 1086, 1059, 1028 cm−1. HRMS (ESI): *m*/*z* [M <sup>−</sup> H]<sup>−</sup> calcd. for C27H27Cl2O14S 677.0504, found 677.0501.

*2-(2,3,4-Tri-O-acetyl-*β*-*d*-xylopyranosyl-1-thio)-6,7-dichloro-3,5,8-trimethoxy-1,4-naphthoquinone* (**14c**); yield 263 mg (86.5%), dark orange solid, *Rf* 0.52 (A), m.p. 132–134 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 2.04 (s, 3H, COCH3), 2.07 (s, 3H, COCH3), 2.10 (s, 3H, COCH3), 3.36 (dd, 1H, *J* = 11.8, 8.6 Hz, H-5- a), 3.97 (s, 3H, -OCH3), 3.98 (s, 3H, -OCH3), 4.15 (s, 3H, -OCH3), 4.18 (dd, 1H, *J* = 11.8, 5.0 Hz, H-5- b), 4.95 (m, 1H, H-4- ), 5.04 (t, 1H, *J* = 8.2 Hz, H-2- ), 5.22 (t, 1H, *J* = 8.2 Hz, H-3- ), 5.57 (d, 1H, *J* = 8.2 Hz, H-1- ). 13C-NMR(125 MHz, CDCl3), <sup>δ</sup>: 20.7 (3 <sup>×</sup> COCH3), 61.3 (-OCH3), 62.3 (2×-OCH3), 65.2 (C-5- ), 68.5 (C-4- ), 70.7 (C-2- ), 71.9 (C-3- ), 81.3 (C-1- ), 124.1, 125.4, 127.6 (C-2), 136.2, 136.9, 152.8, 153.0, 159.1 (C-3), 169.4 (COCH3), 169.7 (COCH3), 169.9 (COCH3), 176.7, 179.7. IR (CHCl3): 3054, 3019, 3006, 2944, 2857, 1754, 1671, 1580, 1547, 1459, 1440, 1380, 1326, 1304, 1246, 1190, 1114, 1067, 1029 cm<sup>−</sup>1. HRMS (ESI): *m*/*z* [M − H]<sup>−</sup> calcd. for C24H23Cl2O12S 605.0293, found 605.0291.

*2-(2,3,4-Tri-O-acetyl-*α*-*l*-arabinopyranosyl-1-thio)-6,7-dichloro-3,5,8-trimethoxy-1,4-naphthoquinone* (**14d**); yield 276 mg (90.8%), dark orange solid, *Rf* 0.50 (A), m.p. 79–81 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 2.07 (s, 3H, COCH3), 2.11 (s, 6H, 2 × COCH3), 3.63 (dd, 1H, *J* = 12.7, 1.9 Hz, H-5- a), 3.96 (s, 3H, -OCH3), 3.98 (s, 3H, -OCH3), 4.06 (dd, 1H, *J* = 12.7, 4.2 Hz, H-5- b), 4.16 (s, 3H, -OCH3), 5.16 (dd, 1H, *J* = 8.3, 3.4 Hz, H-3- ), 5.28 (m, 1H, H-4- ), 5.31 (t, 1H, *J* = 8.0 Hz, H-2- ), 5.57 (d, 1H, *J* = 8.0 Hz, H-1- ). 13C-NMR(125 MHz, CDCl3), δ: 20.7 (COCH3), 20.8 (COCH3), 20.8 (COCH3), 61.3 (-OCH3), 62.3 (2 × -OCH3), 65.6 (C-5- ), 67.5 (C-4- ), 69.2 (C-2- ), 70.3 (C-3- ), 81.6 (C-1- ), 124.1, 125.5, 128.0 (C-2), 136.1, 136.9, 152.8, 153.0, 158.9 (C-3), 169.4 (COCH3), 169.9 (COCH3), 170.2 (COCH3), 176.7, 179.8. IR (CHCl3): 3054, 3027, 3005, 2943, 2856, 1748, 1670, 1580, 1546, 1459, 1440, 1380, 1326, 1304, 1247, 1225, 1190, 1113, 1087, 1060, 1028 cm<sup>−</sup>1. HRMS (ESI): *<sup>m</sup>*/*<sup>z</sup>* [M <sup>−</sup> H]<sup>−</sup> calcd. for C24H23Cl2O12S 605.0293, found 605.0289.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d*-glucopyranosyl-1-thio)-8-hydroxy-3-methoxy-1,4-naphthoquinone* (**15a**); yield 210 mg (73.9%), orange solid, *Rf* 0.46 (A), m.p. 158–161 ◦C. 1H-NMR (700 MHz, CDCl3): δ 1.93 (s, 3H, COCH3), 2.02 (s, 3H, COCH3), 2.03 (s, 3H, COCH3), 2.09 (s, 3H, COCH3), 3.72 (m, 1H, H-5- ), 4.08 (dd, 1H, *J* = 12.4, 2.0 Hz, H-6- a), 4.15 (dd, 1H, *J* = 12.4, 5.5 Hz, H-6- b), 4.29 (s, 3H, -OCH3), 5.08 (t, 1H, *J* = 9.7 Hz, H-4- ), 5.11 (t, 1H, *J* = 10.1 Hz, H-2- ), 5.27 (t, 1H, *J* = 9.3 Hz, H-3- ), 5.50 (d, 1H, *J* = 10.1 Hz, H-1- ), 7.26 (dd, 1H, *J* = 7.4, 1.2 Hz, H-7), 7.59 (dd, 1H, *J* = 8.0, 7.4 Hz, H-6), 7.61 (dd, 1H, *J* = 8.0, 1.2 Hz, H-5), 12.03 (s, 1H, C8OH). 13C-NMR(176 MHz, CDCl3): δ 20.4 (COCH3), 20.5 (COCH3), 20.6 (COCH3), 20.7 (COCH3), 62.1 (C-6- , -OCH3), 68.3 (C-4- ), 71.3 (C-2- ), 73.9 (C-3- ), 76.0 (C-5- ), 81.7 (C-1- ), 114.3 (C-9), 119.7 (C-5), 125.0 (C-7), 126.0 (C-2), 131.3 (C-10), 135.8 (C-6), 160.5 (C-3), 161.2 (C-8), 169.3 (COCH3), 169.4 (COCH3), 170.2 (COCH3), 170.5 (COCH3), 178.4 (C-4), 187.7 (C-1). IR (CHCl3): 3053, 3007, 2953, 1756, 1669, 1630, 1580, 1559, 1458, 1369, 1313, 1250, 1191, 1162, 1077, 1050 cm<sup>−</sup>1. HRMS (ESI): *<sup>m</sup>*/*<sup>z</sup>* [M <sup>−</sup> H]<sup>−</sup> calcd. for C25H25O13S 565.1021, found 565.1016.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d*-galactopyranosyl-1-thio)-8-hydroxy-3-methoxy-1,4-naphthoquinone* (**15b**); yield 203 mg (71.4%), orange solid, *Rf* 0.46 (A), m.p. 190–193 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 1.91 (s, 3H, COCH3), 1.99 (s, 3H, COCH3), 2.10 (s, 3H, COCH3), 2.15 (s, 3H, COCH3), 3.92 (m, 1H, H-5- ), 4.06 (m, 2H, H-6- a, H-6- b), 4.30 (s, 3H, -OCH3), 5.10 (dd, 1H, *J* = 9.9, 3.5 Hz, H-3- ), 5.32 (t, 1H, *J* = 10.0 Hz, H-2- ), 5.43 (m, 1H, H-4- ), 5.46 (d, 1H, *J* = 10.0 Hz, H-1- ), 7.26 (dd, 1H, *J* = 7.7, 1.5 Hz, H-7), 7.58 (dd, 1H, *J* = 7.7, 7.5 Hz, H-6), 7.61 (dd, 1H, *J* = 7.5, 1.5 Hz, H-5), 12.04 (s, 1H, C8OH). 13C-NMR(125 MHz, CDCl3), δ: 20.4 (COCH3), 20.5 (COCH3), 20.6 (COCH3), 20.8 (COCH3), 61.6 (C-6- ), 62.1 (-OCH3), 67.3 (C-4- ), 68.4 (C-2- ), 71.9 (C-3- ), 74.8 (C-5- ), 82.5 (C-1- ), 114.3 (C-9), 119.6 (C-5), 125.0 (C-7), 126.2 (C-2), 131.4 (C-10), 135.8 (C-6), 160.5 (C-3), 161.3 (C-8), 169.6 (COCH3), 170.0 (COCH3), 170.2 (COCH3), 170.3 (COCH3), 178.5 (C-4), 187.7 (C-1). IR (CHCl3): 3055, 3019, 2954, 1751, 1669, 1630, 1580, 1559, 1458, 1441, 1370, 1312, 1249, 1193, 1162, 1080, 1053 cm−1. HRMS (ESI): *m*/*z* [M <sup>−</sup> H]<sup>−</sup> calcd. for C25H25O13S 565.1021, found 565.1021.

*2-(2,3,4-Tri-O-acetyl-*β*-*d*-xylopyranosyl-1-thio)-8-hydroxy-3-methoxy-1,4-naphthoquinone* (**15c**); yield 205 mg (82.6%), orange solid, *Rf* 0.50 (A), m.p. 133–135 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 2.04 (s, 3H, COCH3), 2.08 (s, 3H, COCH3), 2.11 (s, 3H, COCH3), 3.41 (dd, 1H, *J* = 11.9, 8.1 Hz, H-5- a), 4.25 (dd, 1H, *J* = 11.9, 4.8 Hz, H-5- b), 4.29 (s, 3H, -OCH3), 4.95 (m, 1H, H-4- ), 5.05 (t, 1H, *J* = 7.8 Hz, H-2- ), 5.21 (t, 1H, *J* = 7.8 Hz, H-3- ), 5.51 (d, 1H, *J* = 7.9 Hz, H-1- ), 7.26 (dd, 1H, *J* = 8.0, 1.7 Hz, H-7), 7.57 (dd, 1H, *J* = 8.0, 7.5 Hz, H-6), 7.60 (dd, 1H, *J* = 7.5, 1.5 Hz, H-5), 12.05 (s, 1H, C8OH). 13C-NMR(125 MHz, CDCl3), δ: 20.7 (3 × COCH3), 62.1 (-OCH3), 64.9 (C-5- ), 68.3 (C-4- ), 70.6 (C-2- ), 71.5 (C-3- ), 82.7 (C-1- ), 114.4 (C-9), 119.6 (C-5), 125.0 (C-7), 126.0 (C-2), 131.4 (C-10), 135.8 (C-6), 161.3 (C-8), 161.4 (C-3), 169.4 (COCH3), 169.7 (COCH3), 169.8 (COCH3), 178.8 (C-4), 187.7 (C-1). IR (CHCl3): 3056, 2953, 1752, 1671, 1630, 1580, 1558, 1458, 1371, 1313, 1249, 1240, 1208, 1163, 1076 cm<sup>−</sup>1. HRMS (ESI): *m*/*z* [M <sup>−</sup> H]<sup>−</sup> calcd. for C22H21O11S 493.0810, found 493.0805.

*2-(2,3,4-Tri-O-acetyl-*α*-*l*-arabinopyranosyl-1-thio)-8-hydroxy-3-methoxy-1,4-naphthoquinone* (**15d**); yield 197 mg (79.4%), orange solid, *Rf* 0.50 (A), m.p. 84–86 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 2.10 (s, 3H, COCH3), 2.12 (s, 6H, 2 × COCH3), 3.65 (dd, 1H, *J* = 12.5, 2.5 Hz, H-5- a), 4.14 (dd, 1H, *J* = 12.5, 4.9 Hz, H-5- b), 4.30 (s, 3H, -OCH3), 5.17 (dd, 1H, *J* = 7.9, 3.4 Hz, H-3- ), 5.28 (m, 1H, H-4- ), 5.32 (t, 1H, *J* = 7.5 Hz, H-2- ), 5.48 (d, 1H, *J* = 7.5 Hz, H-1- ), 7.26 (dd, 1H, *J* = 7.8, 1.6 Hz, H-7), 7.57 (dd, 1H, *J* = 7.8, 7.5 Hz, H-6), 7.60 (dd, 1H, *J* = 7.5, 1.6 Hz, H-5), 12.06 (s, 1H, C8OH). 13C-NMR(125 MHz, CDCl3), δ: 20.7 (COCH3), 20.8 (COCH3), 20.9 (COCH3), 62.1 (-OCH3), 64.7 (C-5- ), 67.2 (C-4- ), 69.4 (C-2- ), 70.0 (C-3- ), 82.9 (C-1- ), 114.4 (C-9), 119.6 (C-5), 125.0 (C-7), 126.5 (C-2), 131.3 (C-10), 135.8 (C-6), 161.2 (C-3), 161.3 (C-8), 169.4 (COCH3), 169.8 (COCH3), 170.1 (COCH3), 178.8 (C-4), 187.7 (C-1). IR (CHCl3): 3054, 3006, 1748, 1671, 1629, 1580, 1558, 1458, 1372, 1313, 1250, 1162, 1106, 1078, 1061 cm<sup>−</sup>1. HRMS (ESI): *<sup>m</sup>*/*<sup>z</sup>* [M <sup>−</sup> H]<sup>−</sup> calcd. for C22H21O11S 493.0810, found 493.0808.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d*-glucopyranosyl-1-thio)-5-hydroxy-3-methoxy-1,4-naphthoquinone* (**16a**); yield 248 mg (87.3%), red solid, *Rf* 0.46 (A), m.p. 159–161 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 1.93 (s, 3H, COCH3), 2.01 (s, 3H, COCH3), 2.02 (s, 3H, COCH3), 2.08 (s, 3H, COCH3), 3.73 (m, 1H, H-5- ), 4.06 (dd, 1H, *J* = 12.4, 2.3 Hz, H-6- a), 4.16 (dd, 1H, *J* = 12.4, 5.2 Hz, H-6- b), 4.22 (s, 3H, -OCH3), 5.09 (dd, 1H, *J* = 10.1, 4.2 Hz, H-4- ), 5.11 (dd, 1H, *J* = 10.1, 4.1 Hz, H-2- ), 5.27 (t, 1H, *J* = 9.3 Hz, H-3- ), 5.67 (d, 1H, *J* = 10.1 Hz, H-1- ), 7.24 (dd, 1H, *J* = 8.1, 1.4 Hz, H-6), 7.59 (dd, 1H, *J* = 8.1, 7.5 Hz, H-7), 7.62 (dd, 1H, *J* = 7.5, 1.4 Hz, H-8), 11.72 (s, 1H, C5OH). 13C-NMR(125 MHz, CDCl3), <sup>δ</sup>: 20.5 (2 <sup>×</sup> COCH3), 20.6 (2 <sup>×</sup> COCH3), 62.0 (-OCH3, C-6- ), 68.3 (C-4- ), 71.2 (C-2- ), 74.0 (C-3- ), 75.9 (C-5- ), 81.1 (C-1- ), 114.1 (C-10), 119.7 (C-8), 124.4 (C-6), 130.1 (C-2), 132.3 (C-9), 136.5 (C-7), 158.6 (C-3), 161.8 (C-5), 169.3 (COCH3), 169.4 (COCH3), 170.1 (COCH3), 170.5 (COCH3), 181.3 (C-1), 183.5 (C-4). IR (CHCl3): 3050, 3004, 2950, 1756, 1661, 1636, 1579, 1560, 1458, 1369, 1240, 1228, 1212, 1192, 1046 cm<sup>−</sup>1. HRMS (ESI): *m*/*z* [M <sup>−</sup> H]<sup>−</sup> calcd. for C25H25O13S 565.1021, found 565.1017.

*2-(2,3,4,6-Tetra-O-acetyl-*β*-*d*-galactopyranosyl-1-thio)-5-hydroxy-3-methoxy-1,4-naphthoquinone* (**16b**); yield 233 mg (82.0%), dark orange solid, *Rf* 0.46 (A), m.p. 83–86 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 1.91 (s, 3H, COCH3), 1.99 (s, 3H, COCH3), 2.09 (s, 3H, COCH3), 2.15 (s, 3H, COCH3), 3.93 (m, 1H, H-5- ), 4.05 (m, 2H, H-6- a, H-6- b), 4.23 (s, 3H, -OCH3), 5.11 (dd, 1H, *J* = 9.9, 3.4 Hz, H-3- ), 5.31 (t, 1H, *J* = 10.0 Hz, H-2- ), 5.43 (m, 1H, H-4- ), 5.64 (d, 1H, *J* = 10.2 Hz, H-1- ), 7.24 (dd, 1H, *J* = 8.2, 1.3 Hz, H-6), 7.59 (dd, 1H, *J* = 8.2, 7.5 Hz, H-7), 7.63 (dd, 1H, *J* = 7.5, 1.3 Hz, H-8), 11.72 (s, 1H, C5OH). 13C-NMR(125 MHz, CDCl3), δ: 20.5 (COCH3), 20.55 (COCH3-), 20.6 (COCH3), 20.7 (COCH3), 61.4 (C-6- ), 62.0 (-OCH3), 67.3 (C-4- ), 68.3 (C-2- ), 71.9 (C-3- ), 74.6 (C-5- ), 81.9 (C-1- ), 114.1 (C-10), 119.7 (C-8), 124.3 (C-6), 130.2 (C-2), 132.3 (C-9), 136.5 (C-7), 158.6 (C-3), 161.8 (C-5), 169.6 (COCH3), 170.0 (COCH3), 170.2 (COCH3), 170.3 (COCH3), 181.2 (C-1), 183.5 (C-4). IR (CHCl3): 3056, 3006, 1751, 1661, 1636, 1579, 1563, 1458, 1371, 1255, 1191, 1171, 1154, 1085, 1049 cm<sup>−</sup>1. HRMS (ESI): *m*/*z* [M <sup>−</sup> H]<sup>−</sup> calcd. for C25H25O13S 565.1021, found 565.1019.

*2-(2,3,4-Tri-O-acetyl-*β*-*d*-xylopyranosyl-1-thio)-5-hydroxy-3-methoxy-1,4-naphthoquinone* (**16c)**; yield 181 mg (73.0%), orange solid, *Rf* 0.50 (A), m.p. 135–137 ◦C. 1H-NMR (500 MHz, CDCl3), δ: 2.04 (s, 3H, COCH3), 2.07 (s, 3H, COCH3), 2.10 (s, 3H, COCH3), 3.40 (dd, 1H, *J* = 11.8, 8.4 Hz, H-5- a), 4.20 (dd, 1H, *J* = 11.8, 5.0 Hz, H-5- b), 4.22 (s, 3H, -OCH3), 4.96 (m, 1H, H-4- ), 5.05 (t, 1H, *J* = 8.2 Hz, H-2- ), 5.22 (t, 1H, *J* = 8.1 Hz, H-3- ), 5.67 (d, 1H, *J* = 8.2 Hz, H-1- ), 7.23 (dd, 1H, *J* = 8.1, 1.3 Hz, H-6), 7.59 (dd, 1H, *J* = 8.1, 7.5 Hz, H-7), 7.63 (dd, 1H, *J* = 7.5, 1.3 Hz, H-8), 11.71 (s, 1H, C5OH). 13C-NMR(125 MHz, CDCl3), δ: 20.7 (3 × COCH3), 62.1 (-OCH3), 65.1 (C-5- ), 68.5 (C-4- ), 70.6 (C-2- ), 71.8 (C-3- ), 82.0 (C-1- ), 114.2 (C-10), 119.8 (C-8), 124.3 (C-6), 130.0 (C-2), 132.3 (C-9), 136.6 (C-7), 159.4 (C-3), 161.8 (C-5), 169.4 (COCH3), 169.7 (COCH3), 169.8 (COCH3), 181.3 (C-1), 183.7 (C-4). IR (CHCl3): 3053, 3007, 2949, 1754, 1661, 1637, 1579, 1563, 1458, 1371, 1248, 1192, 1171, 1070, 1048 cm<sup>−</sup>1. HRMS (ESI): *<sup>m</sup>*/*<sup>z</sup>* [M <sup>−</sup> H]<sup>−</sup> calcd. for C22H21O11S 493.0810, found 493.0811.

*2-(2,3,4-Tri-O-acetyl-*α*-*l*-arabinopyranosyl-1-thio)-5-hydroxy-3-methoxy-1,4-naphthoquinone* (**16d**); yield 189 mg (76.2%), dark orange solid, *Rf* 0.50 (A), m.p. 97–99 ◦C. 1H-NMR(700 MHz, CDCl3), δ: 2.08 (s, 3H, COCH3), 2.11 (s, 3H, COCH3), 2.12 (s, 3H, COCH3), 3.66 (dd, 1H, *J* = 12.6, 2.3 Hz, H-5- a), 4.09 (dd, 1H, *J* = 12.6, 4.4 Hz, H-5- b), 4.23 (s, 3H, -OCH3), 5.16 (dd, 1H, *J* = 8.2, 3.4 Hz, H-3- ), 5.29 (m, 1H, H-4- ), 5.31 (t, 1H, *J* = 7.7 Hz, H-2- ), 5.66 (d, 1H, *J* = 7.7 Hz, H-1- ), 7.23 (dd, 1H, *J* = 8.3, 1.0 Hz, H-6), 7.59 (dd, 1H, *J* = 8.3, 7.5 Hz, H-7), 7.63 (dd, 1H, *J* = 7.5, 1.0 Hz, H-8), 11.72 (s, 1H, C5OH). 13C-NMR (176 MHz, CDCl3), δ: 20.7 (COCH3), 20.8 (COCH3), 20.9 (COCH3), 62.0 (-OCH3), 65.3 (C-5- ), 67.4 (C-4- ), 69.2 (C-2- ), 70.2 (C-3- ), 82.2 (C-1- ), 114.2 (C-10), 119.8 (C-8), 124.3 (C-6), 130.5 (C-2), 132.3 (C-9), 136.6 (C-7), 159.3 (C-3), 161.8 (C-5), 169.5 (COCH3), 169.8 (COCH3), 170.2 (COCH3), 181.4 (C-1), 183.8 (C-4). IR (CHCl3): 3056, 2947, 1748, 1661, 1636, 1579, 1562, 1457, 1371, 1240, 1193, 1170, 1105, 1087, 1066, 1024 cm−1. HRMS (ESI): *m*/*z* [M − H]<sup>−</sup> calcd. for C22H21O11S 493.0810, found 493.0807.
