606
B. Siewert et al. / Bioorg. Med. Chem. 22 (2014) 594–615
1034s cmÀ1
;
1H NMR (500 MHz, CDCl3): d = 7.31–7.27 (m, 2H, CH
6.2.3.9. m-Chlorobenzyl (2
oate (9). Obtained from MA by method A as a colorless solid;
yield: 73%; mp: 110 °C; Rf = 0.37 (n-hexane/ethyl acetate, 6:4);
D = +41.5° (c 0.32, CHCl3); IR (KBr): = 3438br, 2948vs,
2864m, 1724s, 1636w, 1622w, 1608m, 1514s, 1462m, 1386m,
1366m, 1260m, 1228s, 1176m, 1154s, 1122m, 1050s, 1034s cmÀ1
a,3b) 2,3-dihydroxy-olean-12-en-28-
(33)), 6.92–6.86 (m, 2H, CH (34)), 5.30 (dd, J = 3.5, 3.5 Hz, 1H, CH
(12)), 5.05 (d, J = 12.1 Hz, 1H, CHa (31)), 5.00 (d, J = 12.1 Hz, 1H,
CHb (31)), 3.83 (s, 3H, CH3 (36)), 3.71 (ddd, J = 11.1, 9.8, 4.5 Hz,
1H, CH (2)), 3.02 (d, J = 9.5 Hz, 1H, CH (3)), 2.91 (dd, J = 13.8,
4.0 Hz, 1H, CH (18)), 2.00 (dd, J = 12.7, 4.4 Hz, 1H, CHa (1)), 1.97–
1.86 (m, 3H, CHa (16) + CH2 (11)), 1.73 (ddd, J = 13.9, 13.9, 4.2 Hz,
1H, CHa (7)), 1.69–1.51 (m, 6H, CHa (19) + CHa (15) + CHb
(16) + CHa (6) + CHa (22) + CH (9)), 1.50–1.41 (m, 2H, CHb
(7) + CHb (6)), 1.33 (ddd, J = 14.2, 10.4, 8.1 Hz, 1H, CHa (21)),
1.24–1.15 (m, 3H, CHb (22) + CHb (19) + CHb (21)), 1.14 (s, 3H,
CH3 (27)), 1.05 (s, 3H, CH3 (23)), 0.98 (s, 3H, CH3 (25)), 1.04–0.86
(m, 2H, CHb (1) + CHb (15)), 0.94 (s, 3H, CH3 (30)), 0.92 (s, 3H,
CH3 (29)), 0.91–0.85 (m, 1H, CH (5)), 0.85 (s, 3H, CH3 (24)), 0.62
(s, 3H, CH3 (26)) ppm; 13C NMR (125 MHz, CDCl3): d = 177.5
(C28, C@O), 159.4 (C35, COCH3), 143.8 (C13, C@CH), 129.8 (C33,
CHaromat), 128.6 (C32, Cquart.), 122.3 (C12, CH@C), 113.8 (C34, CHaro-
mat), 84.0 (C3, CHOH), 69.0 (C2, CHOH), 65.7 (C31, CH2), 55.3 (C36,
CH3), 47.6 (C5, CH), 46.7 (C17, Cquart), 46.4 (C1, CH2), 46.4 (C9, CH),
45.9 (C19, CH2), 41.7 (C14, Cquart), 41.4 (C18, CH), 39.3 (C8, Cquart),
39.1 (C4, Cquart), 38.3 (C10, Cquart), 33.8 (C21, CH2), 33.1 (C29,
CH3), 32.6 (C7, CH2), 32.3 (C22, CH2), 30.7 (C20, Cquart), 28.6 (C23,
CH3), 27.6 (C15, CH2), 25.9 (C27, CH3), 23.7 (C30, CH3), 23.4 (C16,
CH2), 23.0 (C11, CH2), 18.3 (C6, CH2), 16.9 (C26, CH3), 16.7 (C24,
CH3), 16.6 (C25, CH3) ppm; MS (ESI, MeOH): m/z = 615.5 (44%,
[M+Na]+), 1207.1 (100%, [2M+Na]+); analysis calculated for
[a]
m
;
1H NMR (400 MHz, CDCl3): d = 7.33 (br s, 1H, CH (33)), 7.30–7.25
(m, 1H, CH (36)), 7.26–7.23 (m, 1H, CH (35)), 7.21–7.18 (m, 1H,
CH (37)), 5.29 (dd, J = 3.4, 3.4 Hz, 1H, CH (12)), 5.06 (d,
J = 12.7 Hz, 1H, CHa (31)), 4.98 (d, J = 12.7 Hz, 1H, CHb (31)), 3.73–
3.63 (m, 1H, CH (2)), 2.98 (d, J = 9.0 Hz, 1H, CH (3)), 2.89 (dd,
J = 13.7, 3.9 Hz, 1H, CH (18)), 2.07 (br s, 2H, OH), 2.03–1.92 (m,
1H, CHa (1)), 1.96 (dd, J = 13.1, 13.1, 3.7 Hz, 1H, CHa (16)), 1.88
(br s, 2H, CH2 (11)), 1.76–1.65 (ddd, J = 13.7, 13.7, 4.3 Hz, 1H, CHa
(7)), 1.61–1.57 (m, 1H, CHb (16)), 1.63–1.57 (m, 1H, CHa (19)),
1.57–1.53 (m, 1H, CHa (15)), 1.55–1.47 (m, 2H, CH (9) + CHa (22)),
1.50–1.48 (m, 1H, CHa (6)), 1.46–1.38 (m, 1H, CHb (7)), 1.38–1.28
(m, 2H, CHb (6) + CHa (21)), 1.27 (m, 1H, CHb (22)), 1.22–1.18 (m,
1H, CHb (21)), 1.20–1.11 (m, 1H, CHb (19)), 1.11 (s, 3H, CH3 (27)),
1.05–0.98 (m, 1H, CHb (15)), 1.01 (s, 3H, CH3 (23)), 0.94 (s, 3H,
CH3 (25)), 0.95–0.86 (m, 1H, CHb (1)), 0.91 (s, 3H, CH3 (30)), 0.89
(s, 3H, CH3 (29)), 0.86–0.82 (m, 1H, CH (5)), 0.80 (s, 3H, CH3
(24)), 0.55 (s, 3H, CH3 (26)) ppm; 13C NMR (100 MHz, CDCl3):
d = 177.5 (C@O, C28), 143.8 (C@CH, C13), 138.5 (Caromat, C32),
134.5 (CClaromat, C34), 129.8 (CHaromat, C36), 128.2 (CHaromat, C35),
128.2 (CHaromat, C33), 126.2 (CHaromat, C37), 122.6 (CH@C, C12),
84.1 (CHOH, C3), 69.1 (CHOH, C2), 65.2 (CH2, C31), 55.4 (CH, C5),
47.7 (CH, C9), 46.9 (Cquart, C17), 46.5 (CH2, C1), 46.0 (CH2, C19),
C38H56O5 (592.84): C 76.99, H 9.52; found: C 76.87, H 9.65.
6.2.3.8. o-Chlorobenzyl (2
oate (8). Obtained from MA by method A as a colorless solid;
yield: 82%; mp: 113 °C; Rf = 0.4 (n-hexane/ethyl acetate, 6:4);
D = +35.1° (c 0.32, CHCl3); IR (KBr): = 3374s, 2946vs, 2878s,
a
,3b) 2,3-dihydroxy-olean-12-en-28-
41.9 (Cquart, C14), 41.5 (CH, C18), 39.5 (Cquart, C8), 39.3 (Cquart,
C4), 38.4 (Cquart, C10), 34.0 (CH2, C21), 33.2 (CH3, C29), 32.7 (CH2,
C22), 32.6 (CH2, C7), 30.8 (Cquart, C20), 28.8 (CH3, C23), 27.7 (CH2,
C15), 26.0 (CH3, C27), 23.8 (CH3, C30), 23.6 (CH2, C11), 23.2 (CH2,
C16), 18.5 (CH2, C6), 17.0 (CH3, C26), 16.9 (CH3, C24), 16.7 (CH3,
C25) ppm; MS (ESI, MeOH, source CID): m/z = 619.5 (100%,
[M+Na]+), 1215.1 (95%, [2M+Na]+); analysis calculated for C37H53-
ClO4 (597.27): C 74.40, H 8.94; found: C 74.29, H 9.09.
[a
]
m
2864s, 1726s, 1462s, 1454s, 1386m, 1366m, 1302m, 1260s,
1234m, 1210m, 1194m, 1160s, 1124m, 1094m, 1082m, 1052s,
1032s, 1012m, 752s cmÀ1 1H NMR (400 MHz, CDCl3): d = 7.43
;
(dd, J = 5.5, 3.9 Hz, 1H, CH (37)), 7.40–7.34 (ddd, J = 6.1, 3.6,
3.6 Hz, 1H, CH (35)), 7.27–7.22 (m, 2H, CH (34) + CH (36)), 5.29
(dd, J = 3.3, 3.3 Hz, 1H, CH (12)), 5.18 (d, J = 13.1 Hz, 1H, CHa
(31)), 5.14 (d, J = 13.1 Hz, 1H, CHb (31)), 3.69 (ddd, J = 10.5, 9.6,
3.9 Hz, 1H, CH (2)), 3.00 (d, J = 9.4 Hz, 1H, CH (3)), 2.92 (dd,
J = 13.7, 3.9 Hz, 1H, CH (18)), 2.05–1.93 (m, 1H, CHa (16)), 1.96
(dd, J = 12.0, 3.8 Hz, 1H, CHa (1)), 1.87 (dd, J = 8.8, 3.3 Hz, 2H, CH2
(11)), 1.74 (ddd, J = 13.7, 13.7, 4.3 Hz, 1H, CHa (7)), 1.72–1.67 (m,
1H, CHb (16)), 1.67–1.60 (m, 2H, CHa (19) + CHa (15)), 1.61–1.53
(m, 2H, CH (9) + CHa (22)), 1.55–1.48 (m, 1H, CHa (6)), 1.47–1.40
(m, 1H, CHb (7)), 1.39–1.28 (m, 2H, CHb (6) + CHa (21)), 1.28–1.20
(m, 2H, CHb (22) + CHb (21)), 1.18–1.13 (m, 1H, CHb (19)), 1.13 (s,
3H, CH3 (27)), 1.08–1.02 (m, 1H, CHb (15)), 1.06 (s, 3H, CH3 (23),
0.94 (s, 3H, CH3 (25)), 0.95–0.86 (m, 1H, CHb (1)), 0.93 (s, 3H, CH3
(30)), 0.89 (s, 3H, CH3 (29)), 0.84–0.80 (m, 1H, CH (5)), 0.81 (s,
3H, CH3 (24)), 0.58 (s,s, 3H, CH3 (26)) ppm; 13C NMR (101 MHz,
6.2.3.10. 2,4-Dichlorobenzyl (2
28-oate (10). Obtained from MA by method A as a colorless
solid; yield: 65%; mp: 122 °C; Rf = 0.21 (n-hexane/ethyl acetate,
8:2); [ D = +36.0° (c 0.31, CHCl3); IR (KBr): = 3440br, 3424vs,
a,3b) 2,3-dihydroxy-olean-12-en-
a]
m
2946vs, 2878m, 2864m, 1728s, 1474s, 1464s, 1386m, 1366m,
1260m, 1240m, 1234m, 1208m, 1160s, 1122m, 1104m, 1082m,
;
1052s, 1032s cmÀ1 1H NMR (400 MHz, CDCl3): d = 7.40 (d,
J = 2.2 Hz, 1H, CH (34)), 7.37 (d, J = 8.4 Hz, 1H, CH (37)), 7.23 (dd,
J = 8.2, 2.0 Hz, 1H, CH (36)), 5.27 (br s, 1H, CH (12)), 5.15 (d,
J = 13.1 Hz, 1H, CHa (31)), 5.08 (d, J = 13.1 Hz, 1H, CHb (31)), 3.69
(br s, 1H, CH (2)), 3.00 (d, J = 9.4 Hz, 1H, CH (3)), 2.89 (dd,
J = 13.7, 3.7 Hz, 1H, CH (18)), 1.98 (ddd, J = 13.3, 13.3 Hz, 4.3 Hz,
1H, CHa (16)), 1.98–1.92 (m, 1H, CHa (1)), 1.86 (dd, J = 10.1,
3.3 Hz, 2H, CH2 (11)), 1.72 (ddd, J = 13.8, 13.8, 4.4 Hz, 2H, CHa
(7)), 1.67–1.61 (m, 1H, CHb (16)), 1.65 (dd, J = 14.1, 14.1 Hz, 1H,
CHa (19)), 1.63–1.55 (m, 2H, CHa (15) + CH (9)), 1.57–1.51 (m, 2H,
CHa (6) + CHa (22)), 1.47–1.40 (m, 1H, CHb (7)), 1.38–1.28 (m, 2H,
CHb (6) + CHa (21)), 1.28–1.20 (m, 2H, CHb (22) + CHb (21)), 1.18–
1.13 (m, 1H, CHb (19)), 1.14 (s, 3H, CH3 (27)), 1.05–1.00 (m, 1H,
CHb (15)), 1.02 (s, 3H, CH3 (23)), 0.94 (s, 3H, CH3 (25)), 0.95–0.86
(m, 1H, CHb (1)), 0.93 (s, 3H, CH3 (30)), 0.90 (s, 3H, CH3 (29)),
0.84–0.80 (m, 1H, CH (5)), 0.82 (s, 3H, CH3 (24)), 0.53 (s, 3H, CH3
(26)) ppm; 13C NMR (100 MHz, CDCl3): d = 177.4 (C@O, C28),
143.7 (C@CH, C13), 134.8 (Caromat, C35), 134.7 (Caromat, C33),
132.8 (Caromat, C32), 131.3 (CHaromat, C37), 129.5 (CHaromat, C34),
127.2 (CHaromat, C36), 122.6 (CH@C, C12), 84.1 (CHOH, C3), 69.1
(CHOH, C2), 63.0 (CH2, C31), 55.4 (CH, C5), 47.7 (CH, C9), 47.0
CDCl3): d = 177.5 (C@O, C28), 143.8 (C@CH, C13), 134.2 (Caromat
C13), 133.9 (CClaromat, C33), 130.2 (CHaromat, C35), 129.6 (CHaromat
,
,
C37), 129.4 (CHaromat, C34), 126.9 (CHaromat, C36), 122.5 (CH@C,
C12), 84.0 (CHOH, C3), 69.06 (CHOH, C2), 63.6 (CH2, C31), 55.4
(CH, C5), 47.7 (CH, C9), 47.0 (Cquart, C17), 46.5 (CH2, C1), 46.0
(CH2, C19), 41.8 (Cquart, C14), 41.5 (CH, C18), 39.5 (Cquart, C8), 39.3
(Cquart, C4), 38.4 (Cquart, C10), 34.0 (CH2, C21), 33.2 (CH2, C7), 32.7
(CH2, C22), 32.5 (CH3, C30), 30.8 (Cquart, C20), 28.7 (CH3, C23),
27.7 (CH2, C15), 26.0 (CH3, C27), 23.7 (CH3, C29), 23.6 (CH2, C11),
23.2 (CH2, C16), 18.5 (CH2, C6), 17.0 (CH3, C26), 16.9 (CH3, C24),
16.7 (CH3, C25) ppm; MS (ESI, MeOH, source CID): m/z = 619.7
(100%, [M+Na]+), 1215.2 (95%, [2M+Na]+); analysis calculated for
C37H53ClO4 (597.37): C 74.40, H 8.94; found: C 74.11, H 9.10.