6
Tetrahedron
-
1
purified by flash column chromatography to
compounds.
A
aff
C
or
C
d
EP
the d
T
e
E
sir
D
ed MA17
N
04
U
, 1
S
48
C
6
R
, 1
I
3
P
53, 1260, 764, 696 cm ; HRMS (EI) m/z calcd for
T
+
C
H
31NO
[M ] 545.2355, found 545.2357.
39
2
4
.3.1. 4a. R = 0.45 (20% EtOAc/hexanes); light yellow solid; 51
f
o 1
4
.3.6. 4f. R = 0.34 (20% EtOAc/hexanes); yellow solid; 31 mg;
f
mg; yield 30%; mp 186–187 C; H NMR (CDCl , 300 MHz) δ
7
Hz, 2H), 7.28–7.25 (m, 2H), 7.20–7.16 (m, 2H), 7.11–7.00 (m,
6
3
1
1
1
3
1
o
1
3
yield 42%; mp 210–211 C; H NMR (CDCl , 300 MHz) δ 7.87
3
.76 (dt, J = 7.5, 1.2 Hz, 1H), 7.58–7.51 (m, 1H), 7.48 (d, J = 3.9
(dd, J = 8.4, 1.5 Hz, 1H), 7.69–7.58 (m, 3H), 7.01 (dd, J = 4.8,
1
1
3
1
1
1
1
3
1
.2 Hz, 1H), 6.95 (dd, J = 4.8, 1.2 Hz, 1H), 6.78 (d, J = 3.3 Hz,
H), 6.73 (t, J = 4.2 Hz, 1H), 6.65 (t, J = 4.2 Hz, 1H), 6.60 (d, J =
.3 Hz, 1H), 4.79 (s, 1H), 4.69–4.62 (m, 1H), 3.97 (d, J = 9.9 Hz,
H), 4.79–4.71 (m, 1H), 4.61 (s, 1H), 3.77 (d, J = 10.8 Hz, 1H),
.12–3.04 (m, 1H), 2.74–2.67 (m, 1H), 2.18–1.95 (m, 3H) , 1.75–
13
.68 (m, 1H); C NMR (CDCl , 150 MHz) δ 201.0, 199.2,
3
H), 3.18–3.10 (m, 1H), 2.83–2.76 (m, 1H), 2.15–1.94 (m, 3H) ,
42.8, 141.8, 138.1, 135.5, 135.4, 135.0, 128.34, 128.30, 127.9,
27.5, 127.4, 127.2, 122.6, 122.5, 76.6, 73.3, 67.5, 58.7, 54.2,
1.7, 25.9; IR νmax (KBr) 2924, 1734, 1701, 1593, 1358, 1257,
13
.79–1.73 (m, 1H); C NMR (CDCl , 150 MHz) δ 200.1, 198.7,
3
43.1, 143.0, 142.1, 137.9, 135.7, 135.2, 126.7, 126.4, 125.7,
24.8, 124.3, 123.8, 122.9, 122.7, 72.3, 71.9, 69.4, 54.3, 53.4,
1.4, 25.4; IR νmax (KBr) 2956,2380, 1733, 1700, 1591, 1367,
-
1
100, 938, 765, 699 cm ; HRMS (EI) m/z calcd for C H NO
27
23
2
+
[
M ] 393.1729, found 393.1724.
-1
354, 1257, 752, 710 cm ; HRMS (EI) m/z calcd for
+
C H NO S [M ] 405.0857, found 405.0851.
23
19
2 2
4
.3.2. 4b. R = 0.26 (40% EtOAc/hexanes); yellow solid; 49 mg;
f
o 1
yield 28%; mp 210–211 C; H NMR (CDCl , 300 MHz) δ 7.74
3
4
.3.7. 4g. R = 0.33 (30% EtOAc/hexanes); white solid; 44 mg;
f
o 1
(d, J = 7.2 Hz, 1H), 7.56–7.48 (m, 3H), 7.12 (d, J = 8.7 Hz, 2H),
yield 26%; mp 154–155 C; H NMR (CDCl , 300 MHz) δ 7.94
3
7
4
.05 (d, J = 8.7 Hz, 2H), 6.44 (dd, J = 9.0, 4.8 Hz, 4H), 4.68–
.60 (m, 1H), 4.48 (s, 1H), 3.65 (d, J = 10.5 Hz, 1H), 3.06–2.98
(
(
d, J = 7.5 Hz, 1H), 7.75–7.64 (m, 3H), 6.96–6.93 (m, 2H), 6.24
d, J = 3.3Hz, 1H), 6.09–6.07 (m, 2H), 6.03 (d, J = 3.3 Hz, 1H),
(m, 1H), 2.783 (s, 6H), 2.780 (s, 6H), 2.72–2.66 (m, 1H), 2.13–
4
2
.56–4.49 (m, 2H), 3.76 (d, J = 10.2 Hz, 1H), 3.17–3.09 (m, 1H),
13
1
2
1
5
1
.88 (m, 2H) , 1.71–1.56 (m, 2H); C NMR (CDCl , 150 MHz) δ
13
3
.82–2.75 (m, 1H), 2.16–1.95 (m, 3H), 1.82–1.74 (m, 1H);
C
01.7, 200.1, 149.8, 149.5, 143.2, 142.1, 135.2, 134.7, 129.1,
28.1, 126.0, 123.4, 122.7, 122.4, 112.2, 112.0, 76.5, 73.4, 67.6,
8.4, 54.0, 40.4, 40.3, 31.7, 25.5; IR νmax (KBr) 3695, 2869,
NMR (CDCl , 150 MHz) δ 200.8, 199.9, 153.7, 149.4, 142.4,
1
1
3
42.3, 142.2, 141.5, 135.64, 135.55, 123.2, 122.8, 110.0, 109.9,
07.6, 107.3, 70.5, 66.4, 65.5, 53.6, 52.8, 27.7, 26.7; IR νmax
-
1
733, 1702, 1613, 1524, 1355, 1254, 946, 810 cm ; HRMS (EI)
(
KBr) 2944, 1741, 1707, 1593, 1349, 1257, 1000, 795, 746, 730
+
m/z calcd for C H N O [M ] 479.2573, found 479.2579.
-
1
+
31
33
3
2
cm ; HRMS (EI) m/z calcd for C H NO [M ] 373.1314, found
23
19
4
3
73.1319.
4
.3.3. 4c. R = 0.34 (30% EtOAc/hexanes); white solid; 55 mg;
f
o 1
yield 32%; mp 122–124 C; H NMR (CDCl , 300 MHz) δ 7.75
3
4
.3.8. 4h. R = 0.18 (40% EtOAc/hexanes); brown solid; 68 mg;
f
(
2
(
dd, J = 7.5, 0.9 Hz, 1H), 7.58–7.50 (m, 3H), 7.17 (d, J = 8.7 Hz,
H), 7.09 (d, J = 8.7 Hz, 2H), 6.59 (t, J = 8.7 Hz, 5H), 4.67–4.62
m, 1H), 4.51 (s, 1H), 3.69 (d, J = 10.5 Hz, 1H), 3.64 (s, 6H),
o
1
yield 39%; mp 204–206 C; H NMR (CDCl , 300 MHz) δ 8.10
3
(d, J = 7.8 Hz, 1H), 7.85 (td, J = 8.1, 1.5 Hz, 1H), 7.75 (td, J =
8
1
=
.1, 1.5 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.06 (d, J = 3.6 Hz,
H), 7.03 (d, J = 3.6 Hz, 1H), 6.61 (d, J = 3.8 Hz, 1H), 6.27 (d, J
3.8 Hz, 1H), 4.57 (s, 1H), 4.55–4.49 (m, 1H), 3.84 (d, J = 10.2
13
3
.07–2.99 (m, 1H), 2.70–2.65 (m, 1H), 2.12–1.93 (m, 3H);
C
NMR (CDCl , 75 MHz) δ 201.3, 199.7, 158.8, 158.6, 143.0,
1
1
IR νmax (KBr) 2932, 1739, 1705, 1610, 1513, 1250, 1180, 1031,
8
3
41.9, 135.4, 134.9, 130.3, 129.4, 128.4, 127.7, 122.6, 122.5,
13.6, 113.3, 76.2, 73.4, 67.7, 58.2, 55.0, 54.3, 54.1, 31.7, 25.8;
Hz, 1H), 3.22–3.15 (m, 1H), 2.86–2.79 (m, 1H), 2.22–2.03 (m,
13
3
1
1
5
1
H), 1.89–1.83 (m, 1H); C NMR (CDCl , 150 MHz) δ 197.2,
3
96.9, 156.0, 153.6, 151.30, 151.29, 141.6, 141.5, 136.54,
36.45,124.0, 123.1, 112.1, 112.0, 111.4, 110.9, 69.4, 69.1, 67.6,
4.8, 50.7, 31.2, 26.1 ; IR νmax (KBr) 2971, 1741, 1703, 1498,
-
1
+
31 cm ; HRMS (EI) m/z calcd for C H NO [M ] 453.1940,
29 27 4
found 453.1946.
-
1
353, 1237, 1012, 811, 738 cm ; HRMS (EI) m/z calcd for
4
.3.4. 4d. R = 0.46 (30% EtOAc/hexanes); light orange solid; 35
+
f
C H N O [M ] 463.1016, found 463.1012.
o
1
23 17
3
8
mg; yield 20%; mp 186–188 C; H NMR (CDCl , 300 MHz) δ
3
7
1
=
.98–7.91 (m, 4H), 7.82 (d, J = 7.5 Hz, 1H), 7.66 (t, J = 7.2 Hz,
H), 7.59 (t, J = 7.8 Hz, 1H), 7.49 (d, J = 7.8 Hz, 1H), 7.45 (d, J
8.4 Hz, 2H), 7.34 (d, J = 8.7 Hz, 2H), 4.83–4.78 (m, 1H), 4.70
4
.3.9. 4i. R = 0.34 (30% EtOAc/hexanes); brown oil; 59 mg;
f
o 1
yield 30%; mp 183–185 C; H NMR (CDCl , 300 MHz) δ 7.94
3
(d, J = 7.5 Hz, 1H), 7.76–7.65 (m, 3H), 6.07 (d, J = 3.0 Hz, 1H),
(
(
(
s, 1H), 3.86 (d, J = 10.5 Hz, 1H), 3.11–3.05 (m, 1H), 2.73–2.65
m, 1H), 2.19–2.02 (m, 3H), 1.74–1.67 (m, 1H); C NMR
CDCl , 150 MHz) δ 199.7, 198.1, 147.4, 147.3, 145.8, 142.6,
5
4
2
1
1
1
3
1
.88 (d, J = 3.0 Hz, 1H), 5.63–5.25 (m, 2H), 4.52–4.44 (m, 1H),
.42 (s, 1H), 3.70 (d, J = 10.2 Hz, 1H), 3.15–3.07 (m, 1H), 2.81–
13
3
.74 (m, 1H), 2.14–1.94 (m, 3H), 1.85 (s, 3H), 1.84 (s, 3H),
1
1
2
42.3, 141.4, 136.5, 136.0, 129.3, 128.1, 123.6, 123.3, 123.01,
13
.92–1.74 (m, 1H); C NMR (CDCl , 150 MHz) δ 199.3, 198.1,
3
22.95, 75.7, 73.2, 67.8, 58.2, 54.2, 31.5, 26.4; IR νmax (KBr)
51.7, 151.6, 151.1, 148.5, 142.4, 141.9, 135.3, 134.8, 122.8,
22.7, 108.6, 107.6, 105.9, 105.8, 69.9, 69.2, 66.9, 54.4, 51.2,
1.5, 25.5, 13.1, 13.0; IR νmax (KBr) 3359, 2923, 1744, 1706,
-
1
959, 1738, 1700, 1519, 1346, 1256, 1109, 859, 691 cm ;
+
HRMS (EI) m/z calcd for C H N O [M ] 483.1430, found
4
27
21
3
6
83.1425.
-1
633, 1260, 1021, 787, 749 cm ; HRMS (EI) m/z calcd for
+
C H NO [M ] 401.1627, found 401.1632.
25
23
4
4
.3.5. 4e. R = 0.63 (30% EtOAc/hexanes); white solid; 56 mg;
f
o
1
yield 32%; mp 219–220 C; H NMR (CDCl , 300 MHz) δ 7.80
3
4
.3.10. 4j. R = 0.2 (20% EtOAc/hexanes); orange solid; 43 mg;
f
o 1
(
7
dt, J = 7.5, 0.9 Hz, 1H), 7.59–7.47 (m, 3H), 7.44–7.40 (m, 4H),
.37–7.32 (m, 10H), 7.29–7.24 (m, 4H), 4.82–4.77 (m, 1H), 4.67
s, 1H), 3.83 (d, J = 10.2 Hz, 1H), 3.16–3.08 (m, 1H), 2.79–2.73
yield 26%; mp 152–154 C; H NMR (CDCl , 300 MHz) δ 7.96
3
(d, J = 8.7 Hz, 2H), 7.78 (d, J = 7.5 Hz, 1H), 7.61 (td, J = 7.5, 1.8
(
(
(
Hz, 1H), 7.57–7.49 (m, 2H), 7.38 (d, J = 8.7 Hz, 2H), 7.15 (d, J =
13
m, 1H), 2.21–1.98 (m, 3H), 1.79–1.73 (m, 1H); C NMR
CDCl , 150 MHz) δ 201.0, 199.3, 142.9, 141.9, 140.5, 140.3,
8
1
2
.7 Hz, 2H), 6.58 (d, J = 8.7 Hz, 2H), 4.80–4.73 (m, 1H), 4.54 (s,
3
H), 3.85 (d, J = 10.5 Hz, 1H), 3.65 (s, 3H), 3.08–3.01 (m, 1H),
1
1
7
40.2, 140.0, 137.4, 135.6, 135.1, 134.7, 128.8, 128.63, 128.58,
27.7, 127.2, 127.1, 126.9, 126.8, 126.7, 126.6, 122.8, 122.6,
3.4, 67.7, 58.5, 54.3, 31.7, 26.0; IR νmax (KBr) 2972, 1742,
13
.72–2.65 (m, 1H), 2.20–1.99 (m, 3H), 1.72–1.66 (m, 1H);
C
NMR (CDCl , 150 MHz) δ 200.3, 198.9, 159.0, 147.1, 143.7,
1
3
42.7, 141.6, 135.9, 135.4, 129.4, 129.35, 128.3, 128.2, 123.5,