10
Tetrahedron
ACCEPTED MANUSCRIPT
11), 21.4 (C-23), 19.4 (C-30), 18.9 (C-6), 16.3 (C-25), 15.7 (C-
27), 14.7 (C-26).
Found: C, 76.41; H, 8.48. C40H53NO5 requires C, 76.52; H, 8.51;
Rf (9% EtOAc/hexane) 0.54; [a]D17+54 (c 0.9, CHCl3); νmax
(CHCl3) 1727 (COOMe) cm-1; δH (400 MHz, CDCl3) 8.17 (d, J 8
Hz, 2H, arom), 7.39 (d, J 8 Hz, 2H, arom), 5.74 (s, 1H, H-4ʹ),
5.32 (br s, 1H, H-12), 4.03 (s, 2H, CH2-5ʹ), 3.63 (s, 3H, OMe),
2.34 (d, 1H, J 15.0 Hz, Ha-1), 2.27 (d, 1H, J 11.0Hz, H-18), 2.05-
1.03 (m, 19H, CH, CH2 in pentacyclic skeleton and 1H, Hb-1),
1.21, 1.11, 1.10, 0.94, 0.82 (all s, 3H each, H-23–H-27), 0.95 (d,
J 6 Hz, 3H, H-30), 0.87 (d, J 6 Hz, 3H, H-29). δc (100 MHz,
CDCl3) 178.1 (C-28), 155.9 (C-3), 149.9 (C-5ʹ), 146.7, 146.5,
129.4, 123.7 (Arom), 138.1 (C-13), 125.6 (C-12), 113.8 (C-2),
108.4 (C-4ʹ), 53.4 (C-5), 53.0 (C-18), 51.5 (COOMe), 48.2 (C-
17), 46.1 (C-9), 42.1 (C-14), 39.6 (C-8), 39.1 (C-19), 38.9 (C-
20), 38.3 (C-1), 38.2 (C-10), 36.6 (C-22), 34.6 (C-4), 34.6 (CH2-
5ʹ), 32.4 (C-7), 30.7 (C-21), 29.3 (C-23), 28.1 (C-15), 24.3 (C-
16), 23.5 (C-27), 23.3 (C-11), 21.5 (C-24), 21.2 (C-30), 19.0 (C-
6), 17.1 (C-26), 16.8 (C-25), 15.7 (C-29).
4.3.6. Methyl 5’-(4-cyanobenzyl)furano[3,2-b]lup-20(29)-en-
28-oate (19m). Yield 0.07g (70%), pale yellow powder, mp 128-
130°С. Found: C, 80.77; H, 8.82. C41H53NO3 requires C, 81.01;
H, 8.79; Rf (9% EtOAc/hexane) 0.42; [a]D22+23 (c 0.2, CHCl3);
νmax (CHCl3) 1723 (COOMe) cm-1; δH (400 MHz, CDCl3) 7.59
(d, 2H, J 8.0 Hz, arom), 7.33 (d, 2H, J 8.0 Hz, arom), 5.71 (s, 1H,
H-4'), 4.77, 4.63 (both br s, 2H, H-29),3.98 (s, 2H, CH2-5'), 3.69
(s, 3H, OMe), 3.04 (m, 1H, H-19), 2.36 (d, 1H, J 15 Hz, Ha-1),
2.31-1.07 (m, 21H, CH, CH2 in pentacyclic skeleton and 1H, Hb-
1), 1.71 (s, 3H, H-30), 1.19, 1.10, 1.00, 0.98, 0.85 (all s, 3H each,
H-23–H-27). δc (100 MHz, CDCl3) 176.7 (C-28), 155.8 (C-3),
150.6 (C-20), 150.1 (C-5ʹ), 144.4, 132.2, 129.4, 110.2 (Arom),
119.0 (C≡N), 113.9 (C-2), 109.6 (C-29), 108.4 (C-4ʹ), 56.6 (C-
17), 53.5 (C-5), 51.3 (COOMe), 49.4 (C-18), 49.2 (C-9), 47.0 (C-
19), 42.4 (C-14), 40.7 (C-8), 38.6 (C-1), 38.5 (C-10), 38.4 (C-
13), 36.9 (C-22), 34.8 (C-4), 34.7 (CH2-5ʹ), 33.5 (C-7), 32.1 (C-
16), 30.6 (C-21), 29.8 (C-15), 29.1 (C-24), 25.6 (C-12), 21.4 (C-
11), 21.4 (C-23), 19.4 (C-30), 18.9 (C-6), 16.3 (C-25), 15.7 (C-
27), 14.7 (C-26).
4.3.10. Methyl 5’-(4-cyanophenyl)furano[3,2-b]urs-12-en-28-
oate (21e). Yield 0.08g (76%), white powder, mp 102-104°С.
Found: C, 80.86; H, 8.78. C41H53NO3 requires C, 81.01; H, 8.79;
Rf (9% EtOAc/hexane) 0.42; [a]D17+57 (c 0.7, CHCl3); νmax
(CHCl3) 1723 (COOMe) cm-1; δH (400 MHz, CDCl3) 7.59 (d, J 8
Hz, 2H, arom), 7.33 (d, J 8 Hz, 2H, arom), 5.71 (s, 1H, H-4ʹ),
5.31 (br s, 1H, H-12), 3.98 (s, 2H, CH2-5ʹ), 3.63 (s, 3H, OMe),
2.30 (d, 1H, J 15.0 Hz, Ha-1), 2.25 (d, 1H, J 11.0Hz, H-18), 2.06-
1.03 (m, 19H, CH, CH2 in pentacyclic skeleton and 1H, Hb-1),
1.21, 1.11, 1.10, 0.94, 0.81 (all s, 3H each, H-23–H-27), 0.95 (d,
J 6 Hz, 3H, H-30), 0.87 (d, J 6 Hz, 3H, H-29). δc (100 MHz,
CDCl3) 178.1 (C-28), 155.8 (C-3), 150.1 (C-5ʹ), 144.4, 132.2,
129.4, 110.2 (Arom), 138.1 (C-13), 125.6 (C-12), 119.1 (CN),
113.8 (C-2), 108.3 (C-4ʹ), 53.4 (C-5), 53.0 (C-18), 51.5
(COOMe), 48.2 (C-17), 46.1 (C-9), 42.1 (C-14), 39.5 (C-8), 39.1
(C-19), 38.9 (C-20), 38.3 (C-1), 38.2 (C-10), 36.6 (C-22), 34.7
(C-4), 34.6 (CH2-5ʹ), 32.4 (C-7), 30.7 (C-21), 29.3 (C-23), 28.1
(C-15), 24.3 (C-16), 23.5 (C-27), 23.3 (C-11), 21.5 (C-24), 21.2
(C-30), 19.0 (C-6), 17.1 (C-26), 16.8 (C-25), 15.7 (C-29).
4.3.7. Methyl 5’-(thiophen-2-ylmethyl)furano[3,2-b]urs-12-
en-28-oate (21b). Yield 0.08g (80%), white powder, mp 87-88°С.
Found: C, 77.27; H, 8.89. C38H52O3S requires C, 77.50; H, 8.90;
Rf (9% EtOAc/hexane) 0.53; [a]D17+65 (c 0.8, CHCl3); νmax
(CHCl3) 1724 (COOMe) cm-1; δH (400 MHz, CDCl3) 7.16 (d, J 5
Hz, 1H, arom), 6.95 (m, 1H, arom), 6.88 (m, 1H, arom), 5.78 (s,
1H, H-4ʹ), 5.33 (br s, 1H, H-12), 4.14 (s, 2H, CH2-5ʹ), 3.64 (s,
3H, OMe), 2.35 (d, 1H, J 15.0 Hz, Ha-1), 2.28 (d, 1H, J 11.0Hz,
H-18), 2.07-1.03 (m, 19H, CH, CH2 in pentacyclic skeleton and
1H, Hb-1), 1.25, 1.15, 1.12, 0.96, 0.83 (all s, 3H each, H-23–H-
27), 0.97 (d, J 6 Hz, 3H, H-30), 0.90 (d, J 6 Hz, 3H, H-29). δc
(100 MHz, CDCl3) 178.1 (C-28), 155.3 (C-3), 151.1 (C-5ʹ),
141.2, 126.7, 125.2, 123.9 (Arom), 138.0 (C-13), 125.7 (C-12),
113.7 (C-2), 107.5 (C-4ʹ), 53.4 (C-5), 53.0 (C-18), 51.5
(COOMe), 48.2 (C-17), 46.1 (C-9), 42.1 (C-14), 39.6 (C-8), 39.1
(C-19), 38.9 (C-20), 38.3 (C-1), 38.2 (C-10), 36.7 (C-22), 34.5
(C-4), 32.4 (C-7), 30.7 (C-21), 29.3 (C-23), 29.0 (CH2-5ʹ), 28.1
(C-15), 24.3 (C-16), 23.5 (C-27), 23.3 (C-11), 21.5 (C-24), 21.2
(C-30), 19.0 (C-6), 17.1 (C-26), 16.8 (C-25), 15.7 (C-29).
4.3.11. Methyl 5’-(thiophen-2-ylmethyl)furano[3,2-b]olean-
12-en-28-oate (23b). Yield 0.07g (75%), white powder, mp 87-
89°С. Found: C, 77.31; H, 8.89. C38H52O3S requires C, 77.50; H,
8.90; Rf (9% EtOAc/hexane) 0.55; [a]D17+69 (c 1.0, CHCl3); νmax
(CHCl3) 1725 (COOMe) cm-1; δH (400 MHz, CDCl3) 7.17(d, J 5
Hz, 1H, arom), 6.95 (m, 1H, arom), 6.88 (m, 1H, arom), 5.78 (s,
1H, H-4ʹ), 5.36 (br s, 1H, H-12), 4.13 (s, 2H, CH2-5ʹ), 3.65 (s,
3H, OMe), 2.91 (dd, 1H, J 14.0, 4.0Hz, H-18), 2.31 (d, 1H, J
15.0 Hz, Ha-1), 2.07-1.09 (m, 19H, CH, CH2 in pentacyclic
skeleton and 1H, Hb-1), 1.25, 1.17, 1.15, 0.96, 0.81 (all s, 3H
each, H-23–H-27), 0.95 (s, 3H, H-29), 0.93 (s, 3H, H-30). δc (100
MHz, CDCl3) 178.3 (C-28), 155.3 (C-3), 151.1 (C-5ʹ), 143.7 (C-
13), 141.2, 126.7, 125.2, 123.8 (Arom), 122.5 (C-12), 113.7 (C-
2), 107.5 (C-4ʹ), 53.5 (C-5), 51.6 (COOMe), 46.8 (C-17), 46.2
(C-9), 45.9 (C-19), 41.8 (C-18), 41.4 (C-14), 39.4 (C-8), 38.4 (C-
10), 38.1 (C-1), 34.5 (C-4), 33.9 (C-22), 33.1 (C-30), 32.4 (C-7),
32.1 (C-21), 30.7 (C-20), 29.3 (C-23), 29.0 (CH2-5ʹ), 27.8 (C-15),
25.8 (C-27), 23.6 (C-29), 23.4 (C-11), 23.1 (C-16), 21.5 (C-24),
19.0 (C-6), 16.6 (C-26), 15.5 (C-25).
4.3.8. Methyl 5’-(5-acetyl-thiophen-2-ylmethyl)furano[3,2-
b]urs-12-en-28-oate (21c). Yield 0.07g (74%), pale yellow
powder, mp 98-99°С. Found: C, 76.18; H, 8.64. C40H54O4S
requires C, 76.15; H, 8.63; Rf (9% EtOAc/hexane) 0.2; [a]D17+56
(c 0.9, CHCl3); νmax (CHCl3) 1723 (COOMe); 1662 (COMe) cm-
1; δH (400 MHz, CDCl3) 7.54 (d, J 4 Hz, 1H, arom), 6.88 (d, J 4
Hz, 1H, arom), 5.83 (s, 1H, H-4ʹ), 5.31 (br s, 1H, H-12), 4.13 (s,
2H, CH2-5ʹ), 3.63 (s, 3H, OMe), 2.52 (s, 3H, COMe), 2.34 (d,
1H, J 15.0 Hz, Ha-1), 2.27 (d, 1H, J 11.0Hz, H-18), 2.06-1.03 (m,
19H, CH, CH2 in pentacyclic skeleton and 1H, Hb-1), 1.22, 1.13,
1.11, 0.94, 0.82 (all s, 3H each, H-23–H-27), 0.95 (d, J 6 Hz, 3H,
H-30), 0.88 (d, J 6 Hz, 3H, H-29).δc (100 MHz, CDCl3) 190.6
(COMe), 178.1 (C-28), 155.8 (C-3), 151.3 (C-5ʹ), 149.4, 142.9,
132.8, 126.5 (Arom), 138.1 (C-13), 125.6 (C-12), 113.9 (C-2),
108.1 (C-4ʹ), 53.4 (C-5), 53.0 (C-18), 51.5 (COOMe), 48.2 (C-
17), 46.0 (C-9), 42.1 (C-14), 39.5 (C-8), 39.1 (C-19), 38.9 (C-
20), 38.3 (C-1), 38.2 (C-10), 36.6 (C-22), 34.6 (C-4), 32.4 (C-7),
30.7 (C-21), 29.7 (CH2-5ʹ), 29.3 (C-23), 28.1 (C-15), 26.6
(COMe), 24.3 (C-16), 23.5 (C-27), 23.3 (C-11), 21.5 (C-24), 21.2
(C-30), 19.0 (C-6), 17.1 (C-26), 16.8 (C-25), 15.7 (C-29).
4.3.12. Methyl 5’-(5-acetyl-thiophen-2-ylmethyl)furano[3,2-
b]olean-12-en-28-oate (23c). Yield 0.08g (78%), pale yellow
powder, mp 92-94°С. Found: C, 75.96; H, 8.68. C40H54O4S
requires C, 76.15; H, 8.63; Rf (9% EtOAc/hexane) 0.2; [a]D17+59
(c 0.9, CHCl3); νmax (CHCl3) 1724 (COOMe); 1662 (COMe) cm-
1; δH (500 MHz, CDCl3) 7.54 (d, J 4 Hz, 1H, arom), 6.88 (d, J 4
Hz, 1H, arom), 5.82 (s, 1H, H-4ʹ), 5.35 (br s, 1H, H-12), 4.13 (s,
2H, CH2-5ʹ), 3.64 (s, 3H, OMe), 2.91 (dd, 1H, J 14.0, 4.0Hz, H-
4.3.9. Methyl 5’-(4-nitrophenyl)furano[3,2-b]urs-12-en-28-
oate(21d). Yield 0.1g (91%), pale yellow powder, mp 104-106°С.