Organic & Biomolecular Chemistry
Communication
3853, 3801, 3741, 3628, 2951, 2916, 2848, 2359, 1456, 1437, (d, J = 7.6 Hz, 1H), 7.78 (dd, J = 8.0, 7.6 Hz, 1H), 7.37 (d, J =
1314, 1292, 1227, 1138, 1081, 992, 927, 761.
7.2 Hz, 1H), 2.59 (s, 3H), 1.37 (s, 9H). 13C NMR (100 MHz,
Methyl 6-(benzyloxymethyl)picolinate (3g).23 56% yield; CDCl3) δ = 164.9, 157.7, 147.4, 137.8, 127.2, 120.0, 57.0, 24.2,
1H NMR (400 MHz, CDCl3) δ = 8.02 (d, J = 7.6 Hz, 1H), 7.84 22.1. HRMS (ESI) calcd for C11H16N2NaO2S ([M + Na]+):
(dd, J = 8.0, 7.6 Hz, 1H), 7.74 (d, J = 7.6 Hz, 1H), 7.27–7.40 263.0830, Found: 263.0825. IR (KBr): νmax (cm−1) = 3853, 3801,
(m, 5H), 4.79 (s, 2H), 4.66 (s, 2H), 3.99 (s, 3H).
Methyl 6-(trityloxymethyl)picolinate (3h). White solid; 78% 1393, 1362, 1259, 1186, 1091, 1072, 994, 848, 826, 753, 601.
yield; mp: 100.4–101.5 °C. 1H NMR (400 MHz, CDCl3) δ =
(R)-N-(tert-Butylsulfinyl)-6-phenylpicolinamide (4e). White
3747, 3710, 3649, 2923, 1734, 1701, 1651, 1595, 1558, 1540,
8.05–7.99 (m, 2H), 7.91–7.85 (m, 1H), 7.51–7.48 (m, 6H), solid; 67% yield; mp: 130.8–131.9 °C; [α]2D0 = −282.0° (c 0.5,
7.32–7.20 (m, 9H), 4.51 (s, 2H), 3.94 (s, 3H). 13C NMR CHCl3). 1H NMR (400 MHz, CDCl3) δ = 9.71–9.62 (m, 1H), 8.17
(100 MHz, CDCl3) δ = 165.6, 160.1, 146.9, 143.6, 137.5, 128.5, (d, J = 8.4 Hz, 1H), 8.00–7.96 (m, 4H), 7.55–7.48 (m, 3H), 1.39
127.9, 127.1, 123.8, 124.4, 87.4, 66.8, 52.8. HRMS (EI) calcd (s, 9H). 13C NMR (100 MHz, CDCl3) δ = 164.7, 156.4, 147.8,
for C27H23NNaO3 ([M + Na]+): 432.1576, Found: 432.1570. 138.6, 137.7, 129.8, 129.0, 126.8, 124.3, 121.3, 57.0, 22.1.
IR (KBr): νmax (cm−1) = 3853, 3837, 3801, 3744, 3675, 3649, HRMS (ESI) calcd for C11H16N2NaO3S ([M + Na]+): 325.0987,
3058, 3031, 2949, 1743, 1724, 1683, 1652, 1591, 1575, 1506, Found: 325.0981. IR (KBr): νmax (cm−1) = 3853, 3747, 3673,
1409, 1447, 1384, 1359, 1313, 1292, 1225, 1193, 1151, 1137, 3629, 3063, 2963, 1702, 1460, 1389, 1185, 1085, 848, 814,
1095, 1076, 1032, 991, 899, 763, 746, 649, 632.
751, 604.
(R)-6-(Allyloxymethyl)-N-(tert-butylsulfinyl)picolinamide
(S)-Methyl 2-phenyl-4,5-dihydrooxazole-4-carboxylate (3i).23 54%
yield; 1H NMR (400 MHz, CDCl3) δ = 7.99–7.96 (m, 2H), (4f). Thick yellow oil; 58% yield; [α]D20 = −52.9° (c 1.0, CHCl3).
7.51–7.46 (m, 1H), 7.42–7.38 (m, 2H), 4.97–4.92 (m, 1H), 1H NMR (400 MHz, CDCl3) δ = 9.52–9.44 (m, 1H), 8.11 (d, J =
4.71–4.66 (m, 1H), 4.60–4.55 (m, 1H) 3.80 (s, 3H).
7.6 Hz, 1H), 7.94 (dd, J = 8.0, 7.6 Hz, 1H), 7.30 (d, J = 7.6 Hz,
(R)-N-(tert-Butylsulfinyl)picolinamide (4a). White solid; 1H), 5.98 (ddd, J = 19.4, 10.8, 5.6 Hz, 1H), 5.37 (d, J = 17.2 Hz,
90% yield; mp: 68.4–70.5 °C; [α]2D0 = −28.3° (c 1.0, CHCl3). 1H), 5.26 (d, J = 10.4 Hz, 1H), 4.68 (s, 2H), 4.15 (d, J = 5.6 Hz,
1H NMR (400 MHz, CDCl3) δ = 9.62–9.54 (m, 1H), 8.64 (d, J = 1H), 1.37 (s, 9H). 13C NMR (100 MHz, CDCl3) δ = 164.3, 157.9,
4.0 Hz, 1H), 8.20 (d, J = 8.0 Hz, 1H), 7.96 (dd, J = 7.6, 7.6 Hz, 146.9, 138.2, 133.9, 125.0, 121.3, 117.3, 72.0, 71.7, 56.8, 21.8.
1H), 7.59 (dd, J = 7.2, 6.4 Hz, 1H), 1.39 (s, 9H). 13C NMR HRMS (ESI) calcd for C14H20N2NaO3S ([M + Na]+): 319.1092,
(100 MHz, CDCl3) δ = 164.2, 148.1, 147.4, 137.4, 127.2, 122.3, Found: 319.1084. IR (KBr): νmax (cm−1) = 3901, 3853, 3801,
56.3, 21.6. HRMS (ESI) calcd for C10H14N2NaO2S ([M + Na]+): 3747, 3649, 1734, 1700, 1685, 1651, 1472, 1395, 1361, 1261,
249.0647, Found: 249.0598. IR (KBr): νmax (cm−1) = 3676, 3413, 1072, 829, 752, 595.
3304, 3058, 2967, 2869, 1703, 1638, 1590, 1449, 1389, 1292,
(R)-6-(Benzyloxymethyl)-N-(tert-butylsulfinyl)picolinamide
1269, 1185, 1106, 1080, 1040, 998, 871, 818, 788, 737, 697, 620. (4g). White solid; 39% yield; mp: 86.5–87.8 °C; [α]2D0 = −289.6°
(R)-N-(tert-Butylsulfinyl)quinoline-2-carboxamide (4b). White (c 0.7, CHCl3). 1H NMR (400 MHz, CDCl3) δ = 9.46–9.38
solid; 58% yield; mp: 155.7–156.2 °C; [α]2D0 = −56.4° (c 1.0, (m, 1H), 8.12 (d, J = 7.6 Hz, 1H), 7.92 (dd, J = 7.6, 7.6 Hz, 1H),
CHCl3). 1H NMR (400 MHz, CDCl3) δ = 9.76–9.70 (m, 1H), 8.35 7.75 (d, J = 8.0 Hz, 1H), 7.41–7.32 (m, 5H), 4.70 (s, 2H), 4.68
(d, J = 8.4 Hz, 1H), 8.27 (d, J = 8.4 Hz, 1H), 8.11(d, J = 8.0 Hz, (s, 2H), 1.35 (s, 9H). 13C NMR (100 MHz, CDCl3) δ = 164.5,
1H), 7.90 (d, J = 8.0 Hz, 1H), 7.81 (dd, J = 7.6, 7.6 Hz, 1H), 7.59 158.0, 147.2, 138.3, 137.5, 128.5, 127.9, 127.7, 125.2, 121.6,
(dd, J = 7.6, 7.2 Hz, 1H), 7.67 (dd, J = 7.6, 7.2 Hz, 1H), 1.42 73.0, 72.3, 57.0, 22.0. HRMS (ESI) calcd for C18H22N2NaO3S
(s, 9H). 13C NMR (100 MHz, CDCl3) δ = 164.8, 147.6, 146.2, ([M + Na]+): 369.1249, Found: 369.1244. IR (KBr): νmax (cm−1) =
137.9, 130.5, 129.8, 129.6, 128.7, 127.7, 118.6, 57.1, 22.0. 3853, 3747, 3673, 3649, 3064, 2286, 1734, 1700, 1651, 1558,
HRMS (ESI) calcd for C14H16N2NaO2S ([M + Na]+): 299.0830, 1540, 1393, 1361, 1261, 1071, 995, 848, 824, 751, 602.
Found: 299.0769. IR (KBr): νmax (cm−1) = 3853, 3747, 2962,
1844, 1700, 1651, 1558, 1540, 1488, 1396, 1362, 1340, 1262, (4h). White solid; 54% yield; mp: 62.0–64.7 °C; [α]2D0 = −342.7°
1099, 1075, 1013, 903, 847, 763.
(c 1.0, CHCl3). 1H NMR (400 MHz, CDCl3) δ = 9.46–9.38
(R)-N-(tert-Butylsulfinyl)-6-(trityloxymethyl)picolinamide
(R)-N-(tert-Butylsulfinyl)isoquinoline-1-carboxamide (4c). White (m, 1H), 8.13 (d, J = 8.4 Hz, 1H), 8.07 (d, J = 7.6 Hz, 1H),
solid; 43% yield; mp: 61.4–64.6 °C; [α]2D0 = −312.0° (c 1.0, 7.87–7.79 (m, 1H), 7.67 (d, J = 7.6 Hz, 1H), 7.56–7.42 (m, 4H),
CHCl3). 1H NMR (400 MHz, CDCl3) δ = 10.00–9.95 (m, 1H), 5.13–5.06 (m, 2H), 4.73 (s, 2H), 1.32 (s, 9H). 13C NMR
9.54 (d, J = 8.0 Hz, 1H), 8.50 (d, J = 5.2 Hz, 1H), 7.90–7.87 (100 MHz, CDCl3) δ = 164.6, 158.5, 147.0, 143.5, 138.2, 128.6,
(m, 2H), 7.78–7.69 (m, 2H), 1.41 (s, 9H). 13C NMR (100 MHz, 128.0, 127.3, 125.0, 121.3, 87.5, 66.4, 57.0, 22.0. HRMS (ESI)
CDCl3) δ = 166.0, 145.2, 140.1, 137.4, 130.7, 129.4, 127.1, 127.0, calcd for C30H30N2NaO3S ([M + Na]+): 521.1875, Found:
126.9, 125.8, 56.8, 22.1. HRMS (ESI) calcd for C14H16N2NaO2S 521.1870. IR (KBr): νmax (cm−1) = 3853, 3747, 3673, 3649, 3566,
([M + Na]+): 299.0830, Found: 299.0824. IR (KBr): νmax (cm−1) = 3478, 3058, 2924, 1734, 1700, 1651, 1594, 1558, 1394, 1362,
3853, 3801, 3747, 3710, 3649, 3056, 2963, 2922, 1698, 1370, 1262, 1216, 1069, 992, 899, 848, 825, 751, 705, 632, 604.
1330, 1083, 847, 749.
(R)-N-((R)-tert-Butylsulfinyl)-2-phenyl-4,5-dihydrooxazole-
(R)-N-(tert-Butylsulfinyl)-6-methylpicolinamide (4d). White 4-carboxamide (4ia). White solid; 30% yield; mp: 140.5–141.4 °C;
1
solid; 18% yield; mp: 127.8–128.7 °C; [α]2D0 = −133.3° (c 0.9, [α]D20 = −155.7° (c 1.0, CHCl3). H NMR (400 MHz, CDCl3) δ =
CHCl3). 1H NMR (400 MHz, CDCl3) δ = 9.62–9.52 (m, 1H), 8.02 8.21–8.15 (m, 1H), 7.96–7.94 (m, 2H), 7.56–7.52 (m, 1H),
This journal is © The Royal Society of Chemistry 2015
Org. Biomol. Chem.