Paper
NJC
18b (78 mg, 47% yield) as colourless syrup. Data for 18b: [a]Y20
=
7.38 (1H, t, J = 7.6, H-70), 7.48 (2H, t, J = 7.6, 2 ꢀ H-60), 7.62 (2H,
ꢁ57.1 (c = 0.01, CH3OH). H-NMR (500 MHz, CD3OD): d 2.26 d, J = 8.0, 2 ꢀ H-50). 13C-NMR (100 MHz, CD3OD): 63.8 (C-6),
(3H, s, 3 ꢀ H-40), 3.77 (1H, dd, J = 12.0, 6.0, H-6a), 3.86 (1H, dd, 63.9 (C-10), 69.8 (C-1), 72.7 (C-4), 77.0 (C-3), 86.6 (C-5), 94.5
J = 12.0, 3.5, H-6b), 4.12 (1H, d, J = 12.5, H-1a), 4.15–4.20 (1H, m, (C-2), 127.3 (C-50), 129.3 (C-20), 130.1 (C-60), 130.5 (C-70), 131.5
H-5), 4.31 (1H, d, J = 12.5, H-1b), 4.56 (1H, d, J = 5.0, H-3), 4.73 (C-40), 142.2 (C-30). IR (CH3OH, cmꢁ1): 3324 (br), 2922 (m), 1438
1
(1H, dd, J = 6.5, 5.0, H-4), 4.80 (1H, d, J = 15.0, H-10a), 4.94 (1H, (s), 1101 (s), 1045 (s), 1006 (s), 943 (m). HRMS required for
d, J = 15.0, H-10b). 13C-NMR (125 MHz, CD3OD): ppm 9.5 (C-40),
C
25H26N3O6 is 464.1816, found 464.1813.
+
62.8 (C-10), 64.0 (C-6), 69.8 (C-1), 72.6 (C-4), 76.9 (C-3), 86.5
(2R,3R,4S,5R)-30-(4-Chlorophenyl)-5-(hydroxymethyl)-4,5-
(C-5), 94.2 (C-2), 130.6 (C-30), 137.8 (C-20). IR (CH3OH, cmꢁ1): dihydro-3H,40H,60H-spiro[furan-2,70-[1,2,3]triazolo[5,1-c][1,4]-
3321 (br), 2993 (m), 1099 (s), 1071 (m). HRMS required for oxazine]-3,4-diol 18f. Chromatography of the crude residue
+
C
10H16N3O5 is 258.1084, found 258.1086.
over silica gel (hexane/ethyl acetate 1/9) gave the pure spiro-
(2R,3R,4S,5R)-30-Ethyl-5-(hydroxymethyl)-4,5-dihydro-3H,40H,60H- nucleoside 18f (145 mg, 63% overall yield) as colourless oil.
spiro[furan-2,70-[1,2,3]triazolo[5,1-c][1,4]oxazine]-3,4-diol 18c. Data for 18f: [a]2D0 = ꢁ31.0 (c = 0.01, CHCl3). 1H-NMR (500 MHz,
Chromatography of the crude residue over silica gel (dichloro- CD3OD): d 3.77 (1H, dd, J = 12.2, 6.0, H-6a), 3.85 (1H, dd,
methane/methanol 9/1) gave the pure spironucleoside 18c J = 12.2, 3.0, H-6b), 4.17 (1H, d, J = 12.5, H-1a), 4.15–4.19 (1H, m,
(90 mg, 51% yield) as colourless syrup. Data for 18c: [a]Y20
=
H-5), 4.35 (1H, d, J = 12.5, H-1b), 4.61 (1H, d, J = 5.0, H-3), 4.75
1
ꢁ34.6 (c = 0.01, CH3OH). H-NMR (400 MHz, CD3OD): d 1.25 (1H, dd, J = 7.0, 5.0, H-4), 5.03 (1H, d, J = 15.5, H-10a), 5.15
(3H, t, J = 7.6, 3 ꢀ H-40), 2.67 (2H, q, J = 7.6, 3 ꢀ H-30), 3.75 (1H, (1H, d, J = 15.5, H-10b), 7.47 (2H, d, J = 8.5, 2 ꢀ H-60), 7.60 (2H, d,
dd, J = 12.0, 6.4, H-6a), 3.84 (1H, dd, J = 12.0, 3.6, H-6b), 4.12 (1H, J = 8.5, 2 ꢀ H-50). 13C-NMR (125 MHz, CD3OD): 62.4 (C-6), 63.5
d, J = 12.4, H-1a), 4.13-4.18 (1H, m, H-5), 4.30 (1H, d, J = 12.4, H- (C-10), 68.4 (C-1), 71.3 (C-4), 75.6 (C-3), 85.2 (C-5), 93.2 (C-2),
1b), 4.55 (1H, d, J = 4.8, H-3), 4.72 (1H, dd, J = 6.4, 4.8, H-4), 4.81 127.3 (C-50), 128.9 (C-60), 129.0 (C-20), 129.4 (C-40), 133.7 (C-70),
(1H, d, J = 15.2, H-10a), 4.96 (1H, d, J = 15.2, H-10b). 13C-NMR 139.7 (C-30). IR (CH3OH, cmꢁ1): 3361 (br), 2922 (m), 1636 (w),
(100 MHz, CD3OD): 13.6 (C-50), 18.9 (C-40), 63.0 (C-6), 64.0 1491 (s), 1090 (s), 1037 (s), 1002 (s), 943 (m), 831 (m). HRMS
(C-10), 70.0 (C-1), 72.7 (C-4), 76.9 (C-3), 86.4 (C-5), 94.2 (C-2), required for C15H17N3O5Cl+ is 354.0851, found 354.0851.
130.2 (C-20), 143.6 (C-30). IR (CH3OH, cmꢁ1): 3392 (br), 2922
(2R,3R,4S,5R)-5-(Hydroxymethyl)-30-(4-methoxyphenyl)-4,5-
(m), 1642 (br), 1101 (s), 1033 (s), 940 (m). HRMS required for dihydro-3H,40H,60H-spiro[furan-2,70-[1,2,3]triazolo[5,1-c][1,4]-
+
C
11H18N3O5 is 272.1241, found 272.1242.
oxazine]-3,4-diol 18g. Chromatography of the crude residue
(2R,3R,4S,5R)-5-(Hydroxymethyl)-30-(naphthalen-2-yl)-4,5- over silica gel (dichloromethane/methanol 95/5) gave the pure
dihydro-3H,40H,60H-spiro[furan-2,70-[1,2,3]triazolo[5,1-c][1,4]- spironucleoside 66g (118 mg, 52% overall yield). White needle
oxazine]-3,4-diol 18d. Chromatography of the crude residue over crystals were obtained after recrystallisation with hexane/
silica gel (hexane/ethyl acetate 15/85) gave the pure spironucleo- Et2O/CH3OH 6 : 3 : 1. Data for 66g: m.p. = 119–120 1C. [a]D20
=
side 18d (120 mg, 50% yield) as white solid. Data for 18d: m.p. = ꢁ51.3 (c = 0.01, CHCl3). 1H-NMR (400 MHz, CD3OD): d 3.80
101–102 1C. [a]2Y0 = ꢁ65.5 (c = 0.01, CHCl3). H-NMR (400 MHz, (1H, dd, J = 12.4, 6.4, H-6a), 3.84 (3H, s, OCH3), 3.88 (1H, dd,
1
CDCl3): d 3.89 (1H, bd, J = 11.6, H-6a), 4.00 (1H, bd, J = 11.6, H-6b), J = 12.0, 3.2, H-6b), 4.18 (1H, d, J = 12.4, H-1a), 4.18–4.22 (1H,
4.09 (1H, br, OH), 4.12 (1H, d, J = 12.8, H-1a), 4.25–4.28 (1H, m, m, H-5), 4.36 (1H, d, J = 12.8, H-1b), 4.63 (1H, d, J = 5.2, H-3),
H-4), 4.37 (1H, d, J = 12.4, H-1b), 4.55 (1H, br, OH), 4.66 (1H, d, 4.78 (1H, dd, J = 6.4, 5.2, H-4), 5.00 (1H, d, J = 15.2, H-10 ), 5.12
a
J = 15.6, H-10a), 4.75 (1H, br, H-3), 4.78 (1H, d, J = 15.2, H-10b), (1H, d, J = 15.2, H-10 ), 7.02 (2H, d, J = 8.8, 2 ꢀ H-60), 7.52 (2H,
b
5.10 (1H, br, OH), 5.26 (1H, br, H-5), 7.30 (1H, d, J = 7.2, H-Naph), d, J = 8.8, 2 ꢀ H-50). 13C-NMR (100 MHz, CD3OD): 55.8 (OCH3),
7.34–7.51 (3H, m, 3 ꢀ H-Naph), 7.93 (3H, t, J = 8.4, 3 ꢀ H-Naph). 63.9 (C-6), 64.0 (C-10), 69.8 (C-1), 72.7 (C-4), 77.0 (C-3), 86.6
13C-NMR (100 MHz, CDCl3): 62.1 (C-6), 62.8 (C-1), 68.9 (C-10), 70.9 (C-5), 94.5 (C-2), 115.5 (C-60), 123.9 (C-30), 128.7 (C-50), 129.0
(C-5), 76.4 (C-3), 85.2 (C-4), 93.4 (C-2), 124.9, 125.3, 126.4, 126.5, (C-20), 142.2 (C-40), 161.2 (C-70). IR (CH3OH, cmꢁ1): 3373 (br),
126.9 (Naph), 127.5 (C-30), 128.6 (Naph), 129.6 (C-20), 130.8, 131.2, 2925 (m), 1615 (m), 1508 (s), 1249 (s), 1097 (s), 1038 (s), 999 (s),
133.9 (Naph), 140.6 (Cipso-Naph). IR (cmꢁ1): 3381 (br), 2992 (w), 943 (m), 833 (m). HRMS required for C16H20N3O6+ is 494.1922,
1211 (s), 1095 (s), 1076 (m), 777 (m), 751 (s). IR (CHCl3, cmꢁ1): 3349 found 494.1922.
(br), 2926 (w), 1103 (s), 1035 (m), 777 (m), 757 (s). HRMS required
for C19H20N3O5+ is 370.1397, found 370.1399.
(2R,3R,4S,5R)-30-(4-Fluorophenyl)-5-(hydroxymethyl)-4,5-dihydro-
3H,40H,60H-spiro[furan-2,70-[1,2,3]triazolo[5,1-c][1,4]oxazine]-3,4-diol
(2R,3R,4S,5R)-5-(Hydroxymethyl)-30-phenyl-4,5-dihydro- 18h. Chromatography of the crude residue over silica gel
3H,40H,60H-spiro[furan-2,70-[1,2,3]triazolo[5,1-c][1,4]oxazine]-3,4- (hexane/ethyl acetate 1/9) gave the pure spironucleoside 18h
diol 18e. Chromatography of the crude residue over silica gel (175 mg, 80% overall yield) as white solid. Data for 18h: [a]D20
=
(hexane/ethyl acetate 1/9) gave the pure spironucleoside 18e ꢁ40.8 (c = 0.01, CHCl3). 1H-NMR (400 MHz, CD3OD): d 3.76
(139 mg, 67% overall yield) as white foam. Data for 18e: [a]D20
=
(1H, dd, J = 12.5, 6.3, H-6a), 3.86 (1H, dd, J = 12.5, 3.3, H-6b), 4.18
ꢁ36.1 (c = 0.01, CHCl3). 1H-NMR (400 MHz, CD3OD): d 3.80 (1H, d, J = 12.2, H-1a), 4.16–4.20 (1H, m, H-5), 4.36 (1H, d, J =
(1H, dd, J = 12.0, 6.4, H-6a), 3.80 (1H, dd, J = 12.4, 3.2, H-6b), 4.20 12.6, H-1b), 4.62 (1H, d, J = 4.9, H-3), 4.76 (1H, t, J = 6.2, H-4),
(1H, d, J = 12.0, H-1a), 4.19–4.23 (1H, m, H-5), 4.38 (1H, d, 5.03 (1H, d, J = 15.3, H-10a), 5.15 (1H, d, J = 15.3, H-10b), 7.21 (2H,
J = 12.4, H-1b), 4.64 (1H, d, J = 5.2, H-3), 4.73 (1H, dd, J = 6.4, 5.2, t, J = 8.7, 2 ꢀ H-60), 7.60 (2H, dd, J = 8.4, 5.4, 2 ꢀ H-50). 13C-NMR
H-4), 5.02 (1H, d, J = 15.2, H-10a), 5.17 (1H, d, J = 15.2, H-10b), (100 MHz, CD3OD): 63.8 (C-6), 63.9 (C-10), 69.8 (C-1), 72.7 (C-4),
18374 | New J. Chem., 2018, 42, 18363--18380 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018