1
70
H. Rojas Cabrera et al. / Tetrahedron: Asymmetry 26 (2015) 163–172
4
.6.2. (R,R)-11-(4-Fluorobenzenesulfonamido)-12-[(S)-pyrroli-
4.6.6. (R,R)-11-(2-Pyridinesulfonamido)-12-[(S)-pyrrolidine-2-
dine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthracene 2
carboxamido]-9,10-dihydro-9,10-ethanoanthracene 6
20
20
White solid (90% yield), mp 219–221 °C. [
a
]
D
= ꢂ83.7 (c 1.4,
): d 1.16–1.54 (m, 4H), 1.81–
.95 (m, 1H), 2.37 (ddd, J = 10.2, 6.0, 6.0 Hz, 1H), 2.74 (ddd,
J = 9.9, 6.6, 6.6 Hz, 1H), 2.94 (t, J = 3.1 Hz, 1H), 3.49 (dd, J = 9.1,
White solid (92% yield), mp 125–127 °C [
CHCl ). H NMR (200 MHz, CDCl ): d 1.42–1.64 (m, 3H), 1.86–
3 3
a
]
D
= ꢂ74.2 (c 1.5,
1
1
CHCl
3
). H NMR (200 MHz, CDCl
3
1
1.98 (m, 1H), 2.62 (dt, J = 10.8, 5.5 Hz, 1H), 2.82 (dt, J = 10.6,
5.4 Hz, 1H), 3.0 (dd, J = 7.3, 7.3 Hz, 1H), 3.51–3.58 (m, 1H), 3.84–
3.88 (m, 1H), 4.24 (d, J = 2.6 Hz, 1H), 4.37 (d, J = 2.2 Hz, 1H),
7.08–7.33 (m, 11H), 7.44–7.50 (m, 1H), 7.81–7.95 (m, 2H), 8.67
4
4
.7 Hz, 1H), 3.76 (dt, J = 8.4, 3.1 Hz, 1H), 4.16 (d, J = 2.4 Hz, 1H),
1
3
.47 (d, J = 2.6 Hz, 1H), 7.07–7.32 (m 12H), 7.80–7.87 (m, 2H).
): d 26.4, 31.1, 47.3, 49.1, 50.0, 56.8, 60.3,
CF = 21.9 Hz), 124.1, 124.4, 125.1, 126.2, 126.5,
CF = 9.7 Hz), 135.7, 137.5, 138.2, 140.0, 140.1, 164.3 (d,
CF = 252.5 Hz) 174.3. IR (KBr) max 3359, 3302, 3147, 2960,
882, 1657, 1590, 1505, 1458, 1419, 1323, 1291, 1270, 1229,
C
1
3
NMR (50 MHz, CDCl
3
3
(d, J = 4.6 Hz, 1H). C NMR (50 MHz, CDCl ): d 25.9, 30.8, 47.0,
2
6
2.3, 116.0 (d,
J
49.0, 50.4, 56.7, 60.0, 61.2, 121.8, 124.9, 125.0, 125.7, 126.4,
126.8, 127.1, 138.0, 138.2, 139.1, 140.4, 140.8, 150.3, 158.1, 174.2
3
1
J
29.7 (d, J
1
m
IR (KBr)
mmax 3282, 3045, 2962, 2873, 2606, 1733, 1648, 1573,
2
1
4
1540, 1509, 1549, 1424, 1370, 1328, 1279, 1230, 1171, 1117,
ꢂ1
+
ꢂ1
+
150, 1092, 1000 cm . HRMS (FAB ) m/z calcd for [C27
92.1757, found 492.1758.
H
27FN
3
O
3
S]:
27 4 3
1080 cm . HRMS (FAB ) m/z calcd for [C26H N O S]: 475.1804,
found 475.1803.
4
.6.3. (R,R)-11-(4-tert-Butylbenzenesulfonamido)-12-[(S)-pyrrol-
4.6.7. (R,R)-11-[(1S,2R)-(7,7-Dimethyl-2-hydroxybicyclo[2.2.1]-
hept-1-yl)methanesulfonamido]-12-[(S)-pyrrolidine-2-carbox-
idine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthracene 3
2
0
White solid (84% yield), mp 229–231 °C. [
a
]
D
= ꢂ86.4 (c 1.5,
): d 1.31 (s, 9H), 1.41–1.52 (m,
H), 1.80–1.94 (m, 1H), 2.44 (ddd, J = 10.1, 6.0, 6.0 Hz, 1H), 2.74
ddd, J = 9.9, 6.5, 6.5 Hz, 1H), 3.02 (t, J = 3.0 Hz, 1H), 3.52 (dd,
J = 9.2, 4.8 Hz, 1H), 3.78 (dt, J = 8.3, 3.1 Hz, 1H), 4.19 (d, J = 2.6 Hz,
amido]-9,10-dihydro-9,10-ethanoanthracene 7
1
20
CHCl
4
(
3
). H NMR (200 MHz, CDCl
3
White solid (88% yield), mp 123–125 °C. [
a
]
D
= ꢂ60.1 (c 1.2,
1
3 3
CHCl ). H NMR (200 MHz, CDCl ): d 0.77 (s, 3H), 1.00 (s, 3H),
1.37–1.85 (m, 10H), 2.55 (dd, J = 6.2, 6.2 Hz, 1H), 2.60 (dd, J = 6.3,
6.3 Hz, 1H), 2.77–2.89 (m, 5H), 3.49–3.44 (m, 3H), 3.63 (dd,
J = 9.0, 5.4 Hz, 1H), 3.92–3.98 (m, 2H), 4.23 (d, J = 3.0 Hz, 1H),
1
2
3
1
1
2
1
1
5
H), 4.46 (d, J = 2.6 Hz, 1H), 7.11–7.30 (m, 10H), 7.44–7.49 (m,
H), 7.73–7.78 (m, 2H). 13C NMR (50 MHz, CDCl
): d 26.4, 31.2,
4.42 (d, J = 3.0 Hz, 1H), 7.61–7.46 (m, 8H). C NMR (50 MHz,
13
3
1.7, 35.7, 47.3, 49.1, 49.8, 56.9, 60.4, 62.2, 124.1, 124.4, 125.1,
25.7, 126.2, 126.4, 126.5, 126.7, 136.7, 137.6, 138.4, 140.2,
55.7, 174.3. IR (KBr) mmax 3354, 3329, 3157, 3066, 3055, 3041,
962, 2902, 2870, 1919, 1734, 1645, 1597, 1498, 1465, 1438,
396, 1371, 1363, 1346, 1300, 1276, 1201, 1166, 1109, 1087,
3
CDCl ): d 20.6, 21.2, 26.7, 28.0, 31.1, 31.3, 39.6, 44.8, 47.4, 49.1,
49.4, 50.8, 51.1, 54.0, 56.9, 60.6, 61.6, 76.4, 124.5, 124.7, 125.1,
125.9, 126.5, 126.7, 126.8, 137.5, 138.2, 139.7, 140.0, 174.1. IR
(KBr)
mmax 3514, 3279, 3071, 3044, 3019, 2950, 2876, 1731, 1653,
1506, 1459, 1370, 1319, 1274, 1237, 1140, 1111, 1075,
ꢂ1
+
ꢂ1
+
049, 1022 cm . HRMS (FAB ) m/z calcd for [C31
30.2477, found 530.2471.
H
36
N
3
O
3
S]:
40 3 4
1025 cm . HRMS (FAB ) m/z calcd for [C31H N O S]: 550.2740,
found 550.2740.
4
.6.4. (R,R)-11-(4-Trifluoromethylbenzenesulfonamido)-12-
4.6.8. (R,R)-11-(N-4-Trifluoromethylbenzenesulfonyl-N-methyl-
amino)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-
[
(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoan-
thracene 4
White solid (73% yield), mp 116–118 °C. [
ethanoanthracene 25
2
0
20
a
]
D
= ꢂ79.8 (c 1.2,
): d 1.0–1.47 (m, 4H), 1.73–1.89
m, 1H), 2.31 (ddd, J = 10.2, 6.0, 6.0 Hz, 1H), 2.68 (ddd, J = 10.0,
White solid (86% yield), mp 96–98 °C. [
a
]
D
= ꢂ62.2 (c 1.0,
1
1
CHCl
3
). H NMR (200 MHz, CDCl
3
3 3
CHCl ). H NMR (200 MHz, CDCl ): d 1.43–1.67 (m, 3H), 1.97–
(
2.01 (m, 3H), 2.25 (s, 3H), 2.58–2.69 (m, 1H), 2.80–2.92 (m, 1H),
3.66 (dd, J = 9.4, 4.8 Hz, 1H), 3.88 (dd, J = 5.1, 2.3 Hz, 1H), 4.14
(d, J = 2.0 Hz, 1H), 4.2 (dd, J = 4.8, 4.8 Hz, 1H), 4.27 (d, J = 2.8 Hz,
6
1
.6, 6.6 Hz, 1H), 2.94 (t, J = 3.1 Hz, 1H), 3.40 (dd, J = 8.8, 4.6 Hz,
H), 3.83 (dt, J = 8.5, 3.0 Hz, 1H), 4.14 (d, J = 2.6 Hz, 1H), 4.51 (d,
J = 2.8 Hz, 1H), 7.10–7.33 (m, 10H), 7.69 (d, J = 8.2 Hz, 2H), 7.95
1H), 7.12–7.44 (m, 8H), 7.76 (d, J = 8.2 Hz, 2H), 7.82 (d,
1
3
13
(
d, J = 8.0 Hz, 2H). C NMR (50 MHz, CDCl
3
): d 26.3, 31.0, 47.2,
CF = 269.0 Hz), 124.0, 124.4,
25.1, 125.7, 126.1, 126.5, 126.6, 127.0, 137.6, 138.1, 140.0,
40.2, 143.3, 174.3. IR (KBr) max 3302, 3047, 2963, 2874, 1647,
542, 1507, 1463, 1403, 1322, 1231, 1163, 1130, 1100,
J = 8.2 Hz, 2H).
47.2, 49.6, 50.6, 60.5, 64.7, 123.2 (q,
3
C NMR (50 MHz, CDCl ): d 26.1, 30.8, 31.4,
9.2, 50.2, 56.3, 60.1, 62.4, 123.0 (q, 1
J
1
JCF = 267.7 Hz), 124.1,
4
1
1
1
1
5
125.0, 125.8, 126.2, 126.3, 126.4, 126.5, 126.6, 126.9, 127.0,
127.1, 127.2, 127.6, 134.1, 134.7, 138.8, 139.2, 141.2, 141.9,
m
175.3. IR (KBr)
mmax 3302, 3071, 3046, 3020, 2951, 2872, 1733,
ꢂ1
+
060 cm
.
27 3 3 3
HRMS (FAB ) m/z calcd for [C28H F N O S]:
1665, 1500, 1463, 1401, 1320, 1225, 1162, 1129, 1090, 1059,
ꢂ1
+
42.1725, found 542.1732.
1015 cm
.
29 3 3 3
HRMS (FAB ) m/z calcd for [C29H F N O S]:
5
56.1882, found 556.1885.
4
.6.5. (R,R)-11-(2,4,6-Triisopropylbenzenesulfonamido)-12-[(S)-
pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthra-
cene 5
4.6.9. (S,S)-11-(4-Trifluorobenzenesulfonamido)-12-[(S)-pyrrol-
idine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthracene 28
20
20
White solid (88% yield), mp 112–114 °C. [
a
]
D
= ꢂ67.1 (c 1.0,
): d 1.11 (d, J = 7.0 Hz, 6H), 1.23
d, J = 7.0 Hz, 6H), 1.24 (d, J = 7.0 Hz, 6H), 1.28–1.68 (m, 3H),
D
White solid (90% yield), mp 104–106 °C. [a] = +29.6 (c 1.2,
1
1
CHCl
3
). H NMR (200 MHz, CDCl
3
3 3
CHCl ). H NMR (200 MHz, CDCl ): d 1.53–1.79 (m, 3H), 1.86–
(
2.07 (m, 3H), 2.50–2.61 (m, 1H), 2.74–2.86 (m, 1H), 3.11 (t,
J = 3.1 Hz, 1H), 3.29 (dd, J = 9.2, 4.6 Hz, 1H), 3.90 (ddd, J = 8.8, 3.0,
3.0 Hz, 1H), 4.10 (d, J = 2.8 Hz, 1H), 4.39 (d, J = 2.8 Hz, 1H), 7.12–
1
6
5
4
1
3
1
3
1
.81–1.95 (m, 4H), 2.41 (dt, J = 9.8, 6.2 Hz, 1H), 2.75 (dt, J = 10.0,
.6 Hz, 1H), 2.88 (hp, J = 7.0 Hz, 1H), 3.33 (b, 1H), 3.57 (dd, J = 9.0,
.0 Hz, 1H), 3.78 (dt, J = 8.5, 3.2 Hz, 1H), 4.11 (hp, J = 7.0 Hz, 2H),
.22 (d, J = 2.6 Hz, 1H), 4.59 (d, J = 3.0 Hz, 1H), 6.90–7.34 (m,
7.35, m, 9H), 7.71 (d, J = 8.2 Hz, 2H), 7.96 (d, J = 8.2 Hz, 2H). 13
C
NMR (50 MHz, CDCl
61.5, 123.4 (q, J
3
): d 26.2, 30.8, 47.1, 49.3, 50.2, 56.1, 60.0,
CF = 263.9 Hz), 124.7, 124.9, 125.5, 126.1, 126.2,
126.3, 126.5, 126.9, 127.0, 127.1, 128.0, 133.8, 137.9, 138.7,
140.6, 140.8, 144.3, 174.8. IR (KBr) max 3270, 3073, 2951, 2874,
1732, 1653, 1510, 1461, 1402, 1321, 1244, 1162, 1128, 1098,
1
3
1
0H). C NMR (50 MHz, CDCl
4.7, 47.3, 49.3, 49.8, 56.8, 60.5, 61.5, 123.5, 124.3, 125.2, 126.0,
26.4, 132.7, 137.4, 138.4, 140.4, 149.8, 152.3, 174.3. IR (KBr)
301, 3069, 3022, 2957, 2868, 1733, 1655, 1599, 1506, 1461, 1423,
3
): d 24.3, 25.4, 26.5, 30.2, 31.0,
m
max
m
ꢂ1
+
ꢂ1
+
363, 1319, 1252, 1150, 1109, 1076, 1041 cm . HRMS (FAB ) m/z
S]: 600.3260, found 600.3250.
27 3 3 3
1059, 1015 cm . HRMS (FAB ) m/z calcd for [C28H F N O S]:
calcd for [C36
H
46
3
N O
3
542.1725, found 542.1731.