3.2.2. General Procedure for the Synthesis of Triazole 1–16
The alkynyl esters (1 eq) and the corresponding azide (1 eq) were dissolved in t-BuOH/H2O (1:1), followed by the addition of CuSO4·5H2O (2 mol%) and sodium ascorbate (10 mol%). The mixture was stirred at room temperature for 24 h. The reaction was stopped by adding H2O, extracted with CH2Cl2, dried over anhydrous Na2SO4, concentrated and purified by column chromatography on silica gel (54%–87% yield).
18-((1-Phenyl-1H-1,2,3-triazol-4-yl)methyl)-8,11,13-abietatrienoate (
1). pale yellow resin;
+27 (
c 0.016, CHCl
3); IR ν
max (film) 2928, 2870, 1720, 1461, 1245, 755 cm
−1;
1H-NMR (CDCl
3): δ 8.02 (1H, s, H-3'), 7.72 (2H, d,
J = 7.8 Hz, H-2'' and H-6''), 7.54 (2H, t,
J = 7.8 Hz, H-3'' and H-5''), 7.46 (1H, t,
J = 7.3 Hz, H-4''), 7.14 (1H, d,
J = 8.2 Hz, H-11), 6.98 (1H, dd,
J = 8.2, 1.5 Hz, H-12), 6.84 (1H, d,
J = 1.5 Hz, H-14), 5.30 (2H, s, H-1'), 2.88 (2H, m, H-7), 2.79 (1H, m, H-15), 2.28 (1H, brd,
J = 12.7 Hz, H-1
β), 2.24 (1H, dd,
J = 12.2, 1.2 Hz, H-5), 1.28 (3H, s, H-19), 1.21 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.20 (3H, s, H-20);
13C-NMR (CDCl
3): δ 178.96 (C-18), 147.15 (C-9), 146.13 (C-13), 144.93 (C-2'), 137.34 (C-1''), 135.02 (C-8), 130.21 (2C, C-3'' and C-5''), 129.34 (C-4''), 127.32 (C-14), 124.57 (C-11), 124.33 (C-12), 121.06 (2C, C-2'' and C-6''), 123.64 (C-3'), 58.12 (C-1'), 48.04 (C-4), 45.24 (C-5), 38.29, 37.34, 36.82, 33.85, 30.38, 25.57, 24.38 (2C, C-16 and C-17), 22.09, 18.92, 16.91; EIMS
m/z 458.2462 [M+H]
+ (calcd for C
29H
36N
3O
2, 458.2807).
18-(2-(1-Phenyl-1H-1,2,3-triazol-4-yl)ethyl)-8,11,13-abietatrienoate (
2). colorless resin;
+17 (
c 0.025, CHCl
3); IR ν
max (film) 2930, 2865, 1726, 1470, 1245, 761 cm
−1;
1H-NMR (CDCl
3): δ 7.79 (1H, s, H-4'), 7.63 (2H, d,
J = 7.6 Hz, H-2'' and H-6''), 7.50 (2H, t,
J = 7.6 Hz, H-3'' and H-5''), 7.42 (1H, t,
J = 7.3 Hz, H-4''), 7.16 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.2 Hz, H-12), 6.84 (1H, brs, H-14), 4.43 (2H, t,
J = 6.6 Hz, H-1'), 3.15 (2H, t,
J = 6.6 Hz, H-2'), 2.83 (2H, m, H-7), 2.71 (1H, m, H-15), 2.29 (1H, brd,
J = 12.2 Hz, H-1
β), 2.24 (1H, dd,
J = 12.2, 1.2, H-5), 1.26 (3H, s, H-19), 1.21 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.19 (3H, s, H-20);
13C-NMR (CDCl
3): δ 178.35 (C-18), 146.73 (C-9), 145.68 (C-13), 144.90 (C-3'), 137.03 (C-1''), 134.49 (C-8), 129.71 (2C, C-3'' and C-5''), 128.56 (C-4''), 126.85 (C-14), 124.11 (C-11), 123.90 (C-12), 120.37 (2C, C-2'' and C-6''), 119.70 (C-4'), 63.10 (C-1'), 47.62 (C-4), 44.83 (C-5), 37.96, 36.89, 36.60, 33.38, 29.99, 25.59, 25.14, 23.92 (2C, C-16 and C-17), 21.70, 18.52, 16.50; EIMS
m/z 472.2695 [M+H]
+ (calcd for C
30H
38N
3O
2, 472.2964).
18-((((1-Phenylthio)methyl)-1H-1,2,3-triazol-4-yl)methyl)-8,11,13-abietatrienoate (
3). pale yellow resin;
+33 (
c 0.013, CHCl
3); IR ν
max (film) 2922, 2852, 1714, 1442, 1238, 742 cm
−1;
1H-NMR (CDCl
3): δ 7.59 (1H, s, H-3'), 7.29 (5H, m, Ph), 7.11 (1H, d,
J = 8.1 Hz, H-11), 6.96 (1H, brd,
J = 8.1 Hz, H-12), 6.81 (1H, brs, H-14), 5.50 (2H, s, CH2S), 5.16 (2H, s, H-1'), 2.81 (2H, m, H-7), 2.72 (1H, m, H-15), 2.26 (1H, brd,
J = 12.7 Hz, H-1
β), 2.14 (1H, dd,
J = 12.2, 1.5, Hz, H-5), 1.22 (3H, s, H-19), 1.17 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.16 (3H, s, H-20);
13C-NMR (CDCl
3): δ 178.90 (C-18), 147.05 (C-9), 146.12 (C-13), 143.92 (C-2'), 134.91 (C-8), 132.63 (2C, C-2'' and C-6''), 131.98 (C-1''), 129.88 (2C, C-3'' and C-5''), 129.18 (C-4''), 127.24 (C-14), 124.50 (C-11), 124.30 (C-12), 123.66 (C-3'), 57.93 (C-1'), 54.35 (
CH
2S), 47.96 (C-4), 45.18 (C-5), 38.25, 37.26, 36.78, 33.97, 30.31, 25.46, 24.29 (2C, C-16 and C-17), 22.03, 18.34, 16.77; EIMS
m/z 504.2641 [M+H]
+ (calcd for C
30H
38N
3O
2S, 504.2684).
18-(2-(((1-Phenylthio)methyl)-1H-1,2,3-triazol-4-yl)ethyl)-8,11,13-abietatrienoate (
4). pale yellow resin;
+14 (
c 0.014, CHCl
3); IR ν
max (film) 2928, 2867, 1722, 1440, 1242, 749 cm
−1;
1H-NMR (CDCl
3): δ 7.36 (1H, s, H-4'), 7.29 (5H, m, Ph), 7.14 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.86 (1H, brs, H-14), 5.45 (2H, s, CH
2S), 4.29 (2H, t,
J = 6.6 Hz, H-1'), 3.03 (2H, t,
J = 6.6 Hz, H-2'), 2.82 (2H, m, H-7), 2.70 (1H, m, H-15), 2.28 (1H, brd,
J = 12.7 Hz, H-1
β), 2.12 (1H, dd,
J = 12.2, 1.5 Hz, H-5), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.21 (3H, s, H-19), 1.18 (3H, s, H-20);
13C-NMR (CDCl
3): δ 178.24 (C-18), 146.77 (C-9), 145.74 (C-13), 144.81 (C-3'), 134.54 (C-8), 131.92 (C-1''), 131.79 (2C, C-2'' and C-6''), 129.24 (2C, C-3'' and C-5''), 128.50 (C-4''), 126.87 (C-14), 124.11 (C-11), 123.93 (C-12), 120.95 (C-4'), 63.15 (C-1'), 53.46 (
CH
2S), 47.55 (C-4), 44.82 (C-5), 37.96, 36.85, 36.50, 33.92, 29.91, 25.59, 25.08, 23.97 (2C, C-16 and C-17), 21.57, 18.49, 16.44; EIMS
m/z 518.2164 [M+H]
+ (calcd for C
31H
40N
3O
2S, 518.2841).
18-(3-(1-Phenyl-1H-1,2,3-triazol-4-yl)propanoyloxy)-8,11,13-abietatriene (
5). white resin;
+20 (
c 0.022, CHCl
3); IR ν
max (film) 2925, 2864, 1726, 1463, 1246, 761 cm
−1;
1H-NMR (CDCl
3): δ 7.78 (1H, s, H-5'), 7.70 (2H, d,
J = 7.6 Hz, H-2'' and H-6''), 7.53 (2H, t,
J = 7.6 Hz, H-3'' and H-5''), 7.42 (1H, t,
J = 7.3 Hz, H-4''), 7.16 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.86 (1H, brs, H-14), 3.98 (1H, d,
J = 10.9 Hz, H-18) 3.75 (1H, d,
J = 10.9 Hz, H-18), 3.11 (2H, t,
J = 7.3 Hz, H-3'), 2.86 (2H, m, H-7), 2.81 (1H, m, H-15), 2.79 (2H, t,
J = 7.3 Hz, H-2'), 2.26 (1H, brd,
J = 12.7 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.20 (3H, s, H-20), 0.92 (3H, s, H-19);
13C-NMR (CDCl
3): δ 173.30 (C-1'), 147.51 (C-4'), 147.46 (C-9), 146.02 (C-13), 137.54 (C-1''), 135.06 (C-8), 130.11 (2C, C-3'' and C-5''), 128.96 (C-4''), 127.28 (C-14), 124.71 (C-11), 124.32 (C-12), 120.82 (2C, C-2'' and C-6''), 119.91 (C-5'), 73.16 (C-18), 44.78 (C-5), 38.65, 37.82, 37.20, 35.96, 34.03, 33.84, 30.65, 25.78, 24.39 (2C, C-16 and C-17), 21.46, 19.42, 18.91, 17.84; EIMS
m/z 486.3360 [M+H]
+ (calcd for C
31H
40N
3O
2, 486.3120).
18-(5-(1-Phenyl-1H-1,2,3-triazol-4-yl)pentanoyloxy)-8,11,13-abietatriene (
6). white resin;
+25 (
c 0.014, CHCl
3); IR ν
max (film) 2930, 2864, 1726, 1461, 1248, 761 cm
−1;
1H-NMR (CDCl
3): δ 7.70 (1H, s, H-7'), 7.71 (2H, d,
J = 7.4 Hz, H-2'' and H-6''), 7.53 (2H, t,
J = 7.4 Hz, H-3'' and H-5''), 7.42 (1H, t,
J = 7.4 Hz, H-4''), 7.18 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.88 (1H, brs, H-14), 3.97 (1H, d,
J = 10.9 Hz, H-18) 3.71 (1H, d,
J = 10.9 Hz, H-18), 2.85 (2H, m, H-7), 2.83 (1H, m, H-15), 2.80 (2H, t,
J = 7.3 Hz, H-5'), 2.36 (2H, t,
J = 7.3 Hz, H-2'), 2.27 (1H, brd,
J = 12.9 Hz, H-1
β), 1.23 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.21 (3H, s, H-20), 0.93 (3H, s, H-19);
13C-NMR (CDCl
3): δ 174.13 (C-1'), 148.86 (C-6'), 147.54 (C-9), 146.03 (C-13), 137.66 (C-1''), 135.12 (C-8), 130.09 (2C, C-3'' and C-5''), 128.87 (C-4''), 127.29 (C-14), 124.71 (C-11), 124.31 (C-12), 120.83 (2C, C-2'' and C-6''), 119.33 (C-7'), 72.84 (C-18), 44.68 (C-5), 38.70, 37.84, 37.20, 35.99, 34.47, 33.83, 30.66, 29.19, 25.78, 25.74, 24.94, 24.38 (2C, C-16 and C-17), 19.39, 18.95, 17.91; EIMS
m/z 514.3686 [M+H]
+ (calcd for C
31H
44N
3O
2, 514.3433).
18-(3-(1-Benzyl-1H-1,2,3-triazol-4-yl)propanoyloxy)-8,11,13-abietatriene (
7). pale yellow resin;
+16 (
c 0.039, CHCl
3); IR ν
max (film) 2934, 2867, 1726, 1458, 1240, 727 cm
−1;
1H-NMR (CDCl
3): δ 7.36 (1H, s, H-5'), 7.34 (2H, d,
J = 7.6 Hz, H-2'' and H-6''), 7.24 (2H, t,
J = 7.6 Hz, H-3'' and H-5''), 7.22 (1H, t,
J = 7.3 Hz, H-4''), 7.17 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.88 (1H, brs, H-14), 5.43 (2H, s,
CH2Ph), 3.94 (1H, d,
J = 10.9 Hz, H-18) 3.71 (1H, d,
J = 10.9 Hz, H-18), 3.00 (2H, t,
J = 7.3 Hz, H-3'), 2.85 (2H, m, H-7), 2.80 (1H, m, H-15), 2.70 (2H, t,
J = 7.3 Hz, H-2'), 2.27 (1H, brd,
J = 12.7 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.21 (3H, s, H-20), 0.90 (3H, s, H-19);
13C-NMR (CDCl
3): δ 173.24 (C-1'), 147.47 (C-9), 147.24 (C-4'), 146.02 (C-13), 135.24 (C-1''), 135.07 (C-8), 129.48 (2C, C-3'' and C-5''), 129.06 (C-4''), 128.40 (2C, C-2'' and C-6''), 127.29 (C-14), 124.71 (C-11), 124.33 (C-12), 121.44 (C-5'), 73.06 (C-18), 54.40 (
CH
2Ph), 44.77 (C-5), 38.66, 37.83, 37.19, 35.93, 34.04, 33.84, 30.65, 25.79, 24.40 (2C, C-16 and C-17), 21.51, 19.41, 18.92, 17.83; EIMS
m/z 500.2639 [M+H]
+ (calcd for C
32H
42N
3O
2, 500.3277).
18-(5-(1-Benzyl-1H-1,2,3-triazol-4-yl)pentanoyloxy)-8,11,13-abietatriene (
8). pale yellow resin;
+10 (
c 0.091, CHCl
3); IR ν
max (film) 2934, 2867, 1729, 1458, 1220, 751 cm
−1;
1H-NMR (CDCl
3): δ 7.36 (1H, s, H-7'), 7.34 (2H, d,
J = 7.6 Hz, H-2'' and H-6''), 7.25 (2H, t,
J = 7.6 Hz, H-3'' and H-5''), 7.22 (1H, t,
J = 7.3 Hz, H-4''), 7.19 (1H, d,
J = 8.1 Hz, H-11), 7.00 (1H, brd,
J = 8.1 Hz, H-12), 6.90 (1H, brs, H-14), 5.48 (2H, s,
CH
2Ph), 3.95 (1H, d,
J = 10.9 Hz, H-18) 3.70 (1H, d,
J = 10.9 Hz, H-18), 2.85 (2H, m, H-7), 2.80 (1H, m, H-15), 2.69 (2H, t,
J = 7.3 Hz, H-5'), 2.32 (2H, t,
J = 7.3 Hz, H-2'), 2.27 (1H, brd,
J = 12.9 Hz, H-1
β), 1.23 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.22 (3H, s, H-20), 0.94 (3H, s, H-19);
13C-NMR (CDCl
3): δ 174.13 (C-1'), 148.63 (C-6'), 147.55 (C-9), 146.02 (C-13), 135.36 (C-1''), 135.13 (C-8), 129.47 (2C, C-3'' and C-5''), 129.03 (C-4''), 128.37 (2C, C-2'' and C-6''), 127.30 (C-14), 124.73 (C-11), 124.32 (C-12), 121.04 (C-7'), 72.80 (C-18), 54.38 (
CH2Ph), 44.68 (C-5), 38.71, 37.84, 37.19, 35.97, 34.45, 33.83, 30.67, 29.23, 25.81, 24.97, 24.41 (2C, C-16 and C-17), 19.39, 18.95, 17.91; EIMS
m/z 528.4121 [M+H]
+ (calcd for C
34H
46N
3O
2, 528.3590).
18-(3-(((1-Phenylthio)methyl)-1H-1,2,3-triazol-4-yl)propanoyloxy)-8,11,13-abietatriene (
9). yellow resin;
+7 (
c 0.197, CHCl
3); IR ν
max (film) 2931, 2864, 1726, 1442, 1250, 749 cm
−1;
1H-NMR (CDCl
3): δ 7.37 (1H, s, H-5'), 7.31 (5H, m, Ph), 7.20 (1H, d,
J = 8.1 Hz, H-11), 7.02 (1H, brd,
J = 8.1 Hz, H-12), 6.92 (1H, brs, H-14), 5.51 (2H, s, CH
2S), 4.00 (1H, d,
J = 10.9 Hz, H-18) 3.73 (1H, d,
J = 10.9 Hz, H-18), 3.02 (2H, t,
J = 7.3 Hz, H-3'), 2.87 (2H, m, H-7), 2.82 (1H, m, H-15), 2.72 (2H, t,
J = 7.3 Hz, H-2'), 2.28 (1H, brd,
J = 12.7 Hz, H-1
β), 1.25 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.23 (3H, s, H-20), 0.94 (3H, s, H-19);
13C-NMR (CDCl
3): δ 173.11 (C-1'), 147.47 (C-9), 147.37 (C-4'), 146.04 (C-13), 135.08 (C-8), 132.50 (3C, C-1'', C-2'' and C-6''), 129.86 (2C, C-3'' and C-5''), 128.99 (C-4''), 127.31 (C-14), 124.74 (C-11), 124.36 (C-12), 121.09 (C-5'), 73.00 (C-18), 53.96 (
CH
2S), 44.72 (C-5), 38.68, 37.84, 37.23, 35.94, 33.97, 33.86, 30.67, 25.83, 24.44 (2C, C-16 and C-17), 21.49, 19.41, 18.94, 17.89; EIMS
m/z 532.3104 [M+H]
+ (calcd for C
32H
42N
3O
2S, 532.2997).
18-(5-(((1-Phenylthio)methyl)-1H-1,2,3-triazol-4-yl))pentanoyloxy)-8,11,13-abietatriene (
10). yellow resin;
+11 (
c 0.256, CHCl
3); IR ν
max (film) 2937, 2867, 1725, 1467, 1251, 749 cm
−1;
1H-NMR (CDCl
3): δ 7.32 (5H, m, Ph), 7.28 (1H, s, H-7'), 7.21 (1H, d,
J = 8.1 Hz, H-11), 7.03 (1H, brd,
J = 8.1 Hz, H-12), 6.92 (1H, brs, H-14), 5.59 (2H, s, CH
2S), 4.00 (1H, d,
J = 10.9 Hz, H-18), 3.74 (1H, d,
J = 10.9 Hz, H-18), 2.87 (2H, m, H-7), 2.85 (1H, m, H-15), 2.70 (2H, t,
J = 7.3 Hz, H-5'), 2.34 (2H, t,
J = 7.3 Hz, H-2'), 2.32 (1H, brd,
J = 12.9 Hz, H-1
β), 1.25 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.24 (3H, s, H-20), 0.96 (3H, s, H-19);
13C-NMR (CDCl
3): δ 174.08 (C-1'), 148.69 (C-6'), 147.54 (C-9), 146.02 (C-13), 135.12 (C-8), 132.64 (2C, C-2'' and C-6''), 132.48 (C-1''), 129.86 (2C, C-3'' and C-5''), 129.02 (C-4''), 127.31 (C-14), 124.74 (C-11), 124.34 (C-12), 120.71 (C-7'), 72.80 (C-18), 54.04 (
CH
2S), 44.68 (C-5), 38.72, 37.85, 37.21, 35.99, 34.29, 33.87, 30.69, 29.14, 25.82, 25.70, 24.85, 24.43 (2C, C-16 and C-17), 19.41, 18.97, 17.94; EIMS
m/z 560.4263 [M+H]
+ (calcd for C
34H
46N
3O
2S, 560.3310).
18-(3-(1-(4-Anisidyl)-1H-1,2,3-triazol-4-yl)propanoyloxy)-8,11,13-abietatriene (
11). white resin;
+21 (
c 0.017, CHCl
3); IR ν
max (film) 2928, 2864, 1726, 1442, 1257, 833 cm
−1;
1H-NMR (CDCl
3): δ 7.70 (1H, s, H-5'), 7.59 (2H, d,
J = 9.0 Hz, H-2'' and H-6''), 7.16 (1H, d,
J = 8.1 Hz, H-11), 7.00 (2H, d,
J = 9.0 Hz, H-3'' and H-5''), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.86 (1H, brs, H-14), 3.98 (1H, d,
J = 10.9 Hz, H-18), 3.86 (3H, s, PhOMe), 3.75 (1H, d,
J = 10.9 Hz, H-18), 3.10 (2H, t,
J = 7.3 Hz, H-3'), 2.87 (2H, m, H-7), 2.82 (1H, m, H-15), 2.78 (2H, t,
J = 7.3 Hz, H-2'), 2.26 (1H, brd,
J = 12.7 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.20 (3H, s, H-20), 0.93 (3H, s, H-19);
13C-NMR (CDCl
3): δ 173.32 (C-1'), 160.07 (C-4''), 147.46 (C-9), 147.29 (C-4'), 146.01 (C-13), 135.06 (C-8), 131.05 (C-1''), 127.28 (C-14), 124.71 (C-11), 124.32 (C-12), 122.45 (2C, C-2'' and C-6''), 120.09 (C-5'), 115.11 (2C, C-3'' and C-5''), 73.15 (C-18), 56.03 (OMe), 44.79 (C-5), 38.66, 37.83, 37.20, 35.96, 34.08, 33.84, 30.65, 25.78, 24.40 (2C, C-16 and C-17), 21.47, 19.42, 18.92, 17.84; EIMS
m/z 516.4582 [M+H]
+ (calcd for C
32H
42N
3O
3, 516.3226).
18-(5-(1-(4-Anisidyl)-1H-1,2,3-triazol-4-yl)pentanoyloxy)-8,11,13-abietatriene (
12). white resin;
+12 (
c 0.060, CHCl
3); IR ν
max (film) 2937, 2867, 1729, 1461, 1257, 830 cm
−1;
1H-NMR (CDCl
3): δ 7.61 (1H, s, H-7'), 7.60 (2H, d,
J = 8.9 Hz, H-2'' and H-6''), 7.17 (1H, d,
J = 8.1 Hz, H-11), 7.00 (2H, d,
J = 9.0 Hz, H-3'' and H-5''), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.88 (1H, brs, H-14), 3.97 (1H, d,
J = 10.9 Hz, H-18), 3.86 (3H, s, PhOMe), 3.71 (1H, d,
J = 10.9 Hz, H-18), 2.86 (2H, m, H-7), 2.81 (1H, m, H-15), 2.78 (2H, t,
J = 7.3 Hz, H-5'), 2.35 (2H, t,
J = 7.3 Hz, H-2'), 2.27 (1H, brd,
J = 12.9 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.21 (3H, s, H-20), 0.93 (3H, s, H-19);
13C-NMR (CDCl
3): δ 174.15 (C-1'), 160.01 (C-4''), 148.66 (C-6'), 147.54 (C-9), 146.02 (C-13), 135.12 (C-8), 131.17 (C-1''), 127.29 (C-14), 124.71 (C-11), 124.30 (C-12), 122.49 (2C, C-2'' and C-6''), 119.54 (C-7'), 115.10 (2C, C-3'' and C-5''), 72.84 (C-18), 56.03 (OMe), 44.68 (C-5), 38.69, 37.83, 37.19, 35.99, 34.47, 33.83, 30.66, 29.23, 25.79, 25.74, 24.95, 24.38 (2C, C-16 and C-17), 19.39, 18.94, 17.90; EIMS
m/z 544.4256 [M+H]
+ (calcd for C
34H
46N
3O
3, 544.3539).
18-(3-(1-(3-Chlorophenyl)-1H-1,2,3-triazol-4-yl)propanoyloxy)-8,11,13-abietatriene (
13). white resin;
+19 (
c 0.014, CHCl
3); IR ν
max (film) 2928, 2864, 1726, 1460, 1248, 776 cm
−1;
1H-NMR (CDCl
3): δ 7.78 (1H, s, H-5'), 7.76 (1H, s, H-2''), 7.61 (1H, d,
J = 8.0 Hz, H-6''), 7.45 (1H, t,
J = 8.0 Hz, H-5''), 7.39 (1H, d,
J = 8.0 Hz, H-4''), 7.16 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.86 (1H, brs, H-14), 3.98 (1H, d,
J = 10.9 Hz, H-18) 3.75 (1H, d,
J = 10.9 Hz, H-18), 3.11 (2H, t,
J = 7.3 Hz, H-3'), 2.86 (2H, m, H-7), 2.80 (1H, m, H-15), 2.78 (2H, t,
J = 7.3 Hz, H-2'), 2.26 (1H, brd,
J = 12.7 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.20 (3H, s, H-20), 0.92 (3H, s, H-19);
13C-NMR (CDCl
3): δ 173.23 (C-1'), 147.81 (C-4'), 147.45 (C-9), 146.03 (C-13), 138.36 (C-3''), 135.94 (C-1''), 135.04 (C-8), 131.20 (C-5''), 129.00 (C-4''), 127.28 (C-14), 124.71 (C-11), 124.33 (C-12), 121.02 (C-2''), 119.85 (C-5'), 118.72 (C-6''), 73.15 (C-18), 44.74 (C-5), 38.64, 37.82, 37.21, 35.96, 33.90, 33.84, 30.64, 25.77, 24.40 (2C, C-16 and C-17), 21.40, 19.41, 18.91, 17.84; EIMS
m/z 520.2411 [M+H]
+ (calcd for C
31H
39ClN
3O
2, 520.2731).
18-(5-(1-(3-Chlorophenyl)-1H-1,2,3-triazol-4-yl)pentanoyloxy)-8,11,13-abietatriene (
14). pale yellow resin;
+17 (
c 0.012, CHCl
3); IR ν
max (film) 2934, 2864, 1726, 1461, 1241, 782 cm
−1;
1H-NMR (CDCl
3): δ 7.76 (1H, s, H-2''), 7.69 (1H, s, H-5'), 7.63 (1H, d,
J = 8.0 Hz, H-6''), 7.45 (1H, t,
J = 8.0 Hz, H-5''), 7.39 (1H, d,
J = 8.0 Hz, H-4''), 7.17 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.88 (1H, brs, H-14), 3.97 (1H, d,
J = 10.9 Hz, H-18) 3.72 (1H, d,
J = 10.9 Hz, H-18), 2.86 (2H, m, H-7), 2.83 (1H, m, H-15), 2.80 (2H, t,
J = 7.3 Hz, H-5'), 2.35 (2H, t,
J = 7.3 Hz, H-2'), 2.27 (1H, brd,
J = 12.9 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.20 (3H, s, H-20), 0.94 (3H, s, H-19);
13C-NMR (CDCl
3): δ 174.06 (C-1'), 149.16 (C-6'), 147.55 (C-9), 146.04 (C-13), 138.48 (C-3''), 135.91 (C-1''), 135.10 (C-8), 131.16 (C-5''), 128.90 (C-4''), 127.28 (C-14), 124.70 (C-11), 124.30 (C-12), 121.03 (C-2''), 119.19 (C-7'), 118.75 (C-6''), 72.83 (C-18), 44.70 (C-5), 38.73, 37.84, 37.21, 36.00, 34.43, 33.83, 30.65, 29.10, 25.75, 25.68, 24.90, 24.36 (2C, C-16 and C-17), 19.40, 18.94, 17.90; EIMS
m/z 548.4267 [M+H]
+ (calcd for C
33H
43ClN
3O
2, 548.3044).
18-(3-(1-(4-Toluenesulfonyl)-1H-1,2,3-triazol-4-yl)propanoyloxy)-8,11,13-abietatriene (
15). pale yellow resin;
+22 (
c 0.022, CHCl
3); IR ν
max (film) 2934, 2864, 1729, 1461, 1240, 816 cm
−1;
1H-NMR (CDCl
3): δ 7.97 (2H, d,
J = 8.1 Hz, H-2'' and H-6''), 7.91 (1H, s, H-5'), 7.37 (2H, d,
J = 8.1 Hz, H-3'' and H-5''), 7.17 (1H, d,
J = 8.1 Hz, H-11), 6.99 (1H, brd,
J = 8.1 Hz, H-12), 6.88 (1H, brs, H-14), 3.94 (1H, d,
J = 10.9 Hz, H-18) 3.72 (1H, d,
J = 10.9 Hz, H-18), 3.02 (2H, t,
J = 7.3 Hz, H-3'), 2.88 (2H, m, H-7), 2.81 (1H, m, H-15), 2.69 (2H, t,
J = 7.3 Hz, H-2'), 2.43 (3H, s, Ph
Me), 2.27 (1H, brd,
J = 12.7 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.20 (3H, s, H-20), 0.90 (3H, s, H-19);
13C-NMR (CDCl
3): δ 172.82 (C-1'), 147.59 (C-4'), 147.44 (C-9), 146.64 (C-4''), 146.04 (C-13), 135.04 (C-8), 133.59 (C-1''), 130.82 (2C, C-2'' and C-6''), 129.05 (2C, C-3'' and C-5''), 127.30 (C-14), 124.68 (C-11), 124.33 (C-12), 121.43 (C-5'), 73.25 (C-18), 44.76 (C-5), 38.65, 37.81, 37.17, 35.95, 33.84, 33.50, 30.62, 25.77, 24.39 (2C, C-16 and C-17), 21.18, 19.40, 18.89, 17.80; EIMS
m/z 564.3065 [M+H]
+ (calcd for C
32H
42N
3O
4S, 564.2896).
18-(5-(1-(4-Toluenesulfonyl)-1H-1,2,3-triazol-4-yl)pentanoyloxy)-8,11,13-abietatriene (
16). pale yellow resin;
+30 (
c 0.035, CHCl
3); IR ν
max (film) 2937, 2867, 1726, 1451, 1250, 816 cm
−1;
1H-NMR (CDCl
3): δ 7.93 (2H, d,
J = 8.1 Hz, H-2'' and H-6''), 7.72 (1H, s, H-5'), 7.32 (2H, d,
J = 8.1 Hz, H-3'' and H-5''), 7.18 (1H, d,
J = 8.1 Hz, H-11), 7.01 (1H, brd,
J = 8.1 Hz, H-12), 6.89 (1H, brs, H-14), 3.99 (1H, d,
J = 10.9 Hz, H-18) 3.66 (1H, d,
J = 10.9 Hz, H-18), 2.86 (2H, m, H-7), 2.83 (1H, m, H-15), 2.81 (2H, t,
J = 7.3 Hz, H-5'), 2.43 (3H, s, Ph
Me), 2.24 (2H, t,
J = 7.3 Hz, H-2'), 2.20 (1H, brd,
J = 12.9 Hz, H-1
β), 1.22 (6H, d,
J = 6.9 Hz, H-16 and H-17), 1.21 (3H, s, H-20), 0.93 (3H, s, H-19);
13C-NMR (CDCl
3): δ 174.20 (C-1'), 148.65 (C-6'), 147.60 (C-9), 146.10 (C-13), 145.42 (C-4''), 135.18 (C-8), 133.20 (C-1''), 129.98 (2C, C-2'' and C-6''), 128.76 (2C, C-3'' and C-5''), 127.33 (C-14), 124.72 (C-11), 124.33 (C-12), 119.33 (C-7'), 72.73 (C-18), 44.58 (C-5), 38.74, 37.83, 37.23, 35.94, 34.38, 33.83, 30.64, 28.63, 25.77, 25.70, 24.82, 24.40 (2C, C-16 and C-17), 22.08, 19.36, 18.92, 17.90; EIMS
m/z 592.3027 [M+H]
+ (calcd for C
34H
46N
3O
4S, 592.3209).