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Table of contents
Page No
S-6
S-7
S-19
References
S-20
S-21
S-45
11
S-51
19
S-51
S-1
S-2
Entry
Solvent
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
9
10
DME
t-amylOH
DCE
MeOH
MeCN
THF
1,4-dioxane
DMF
IPA
EtOAc
30
30
30
30
30
30
30
30
30
30
24
24
24
24
24
24
24
24
24
24
10
trace
20
14
6
trace
7
3
11
12
13
14
15
16
17
toluene
CHCl3
PhCl
DCE
DCE
MeOH
MeOH
30
30
30
60
80
60
60
24
24
24
24
24
24
24
trace
12
34
36
54
98c
18
19
MeOH
MeOH
60
60
18
12
98c
80c
All reactions were carried out using 2-vinylpyridine 1a (30.0 mg, 0.28 mmol), alkyne 2a (61.0 mg,
0.34 mmol), [Cp*RhCl2]2 (1.8 mg, 0.0028 mmol), Cu(BF4)2.6H2O (49.0 mg, 0.14 mmol) and solvent
(3.0 mL) at indicated temperature for 24 h under 1 atm. O2. bYields were determined by the 1H NMR
integration method using mesitylene as the internal standard. cThe reaction was carried out for MeOH
(1.0 mL).
S-3
S-4
Entry
Solvent
Time (h)
Yield (%)b
t-amylOH
18
10
2
3
4
5
6
7
8
9
10
11
12
EtOH
tert-Butanol
DME
acetone
MeCN
toluene
THF
DCE
2-ethoxyethanol
1,4-dioxane
DMF
18
18
18
18
18
18
18
18
18
18
18
5
30
10
53
12
6
22
trace
trace
13
14
15
16
17
18
19
MeNO2
EtOAc
IPA
DMA
DMSO
EtOAc
EtOAc
18
18
18
18
18
18
18
85
20
trace
37
37c
25d
20
EtOAc
24
99e
21
t-amylOH
18
tracef
All reactions were carried out using 2-vinylpyridine 1a (30.0 mg, 0.28 mmol), alkyne 2a (61.0 mg,
0.34 mmol), [RuCl2(p-cymene)]2 (3.5 mg, 0.0056 mmol), AgBF4 (6.0 mg, 0.028 mmol),
Cu(BF4)2.6H2O (197.0 mg, 0.56 mmol) and solvent (2.0 mL) at 100 oC for 18 h. bYields were
determined by the 1H NMR integration method using mesitylene as the internal standard. cThe reaction
was carried out using Cu(BF4)2.6H2O (98.0 mg, 0.28 mmol). dThe reaction was carried out at 80 oC.
e
The reaction was carried out for 24 h. fThe reaction was carried out using Cu(BF4)2.6H2O (49.0 mg,
To a 50 mL-flask were added 3aa (100 mg, 0.27 mmol), Pd/C (6 mg, 0.027
mmol), and MeOH (10 mL). Hydrogen gas was bubbled through the suspension,
and then the mixture was stirred at 30 C for 16 h under one hydrogen gas
atmosphere. After the reaction time was completed, the mixture was filtered
through a Celite pad and the Celite pad was washed several times with MeOH
(30 mL). The combined filtrate was concentrated in vacuo and the mixture was
separated by column chromatography on a silica gel column using a mixture of
DCM/MeOH (95:5) as eluent to afford the desired pure product 3aa.
S-6
Yellow solid: m.p. 175-177 C; 1H NMR (400 MHz, CDCl3): 8.63 (d, J = 7.6 Hz, 1
H), 8.54-8.49 (m, 2 H), 8.19-8.16 (m, 2 H), 7.77 (td, J = 7.2, 1.6 Hz, 1 H), 7.48-7.43
(m, 3 H), 7.39-7.36 (m, 2 H), 7.22-7.15 (m, 3 H), 7.13-7.11 (m, 2 H); 13C NMR (100
MHz, CDCl3): 143.5 (C), 142.9 (C), 138.7 (C), 138.6 (CH), 136.4 (CH), 135.8 (C),
132.9 (CH), 130.9 (CH), 130.5 (2CH), 129.9 (2CH), 129.6 (C), 129.3 (2CH), 128.5
(2CH), 128.4 (2CH), 127.3 (CH), 124.3 (CH); 11B NMR (160 MHz, CDCl3): -1.28;
19
F NMR (470 MHz, CDCl3): -154.03, -154.08 and secondary isotopic shift (10B,
11
B) of 0.055 ppm; HRMS (FAB+) cal for C21H16N+ 282.1283, found 282.1287; IR
(KBr): 3062, 1643, 1619, 1589, 1496, 1434, 1403, 1334, 1280, 1234, 1056 ( B-F), 848,
771, 717 and 701 cm-1.
Green solid: m.p. 92-94 C; 1H NMR (400 MHz, CDCl3): 8.65 (d, J = 6.8 Hz, 1 H),
8.53-8.50 (m, 2 H), 8.20-8.17 (m, 2 H), 7.78 (t, J = 6.8 Hz, 1 H), 7.27 (d, J = 8.4 Hz, 2
H), 7.22 (d, J = 8.4 Hz, 2 H), 7.14-7.09 (m, 4 H), 2.36 (s, 3 H), 2.24 (s, 3 H);
13
NMR (100 MHz, CDCl3): 143.5 (C), 142.8 (C), 141.3 (C), 138.8 (CH), 138.7 (C),
138.5 (C), 136.3 (CH), 132.9 (C), 132.7 (CH), 130.7 (2CH), 130.3 (2CH), 129.2
(2CH), 129.1 (2CH), 128.5 (CH), 127.1 (CH), 126.7 (C), 124.2 (CH), 21.4 (CH3),
21.1 (CH3); HRMS (FAB+) cal for C23H20N+ 310.1596, found 310.1594; IR (KBr):
2923, 2854, 1643, 1619, 1504, 1434, 1403, 1334, 1280, 1234, 1187, 1056 ( B-F) and
833 cm-1.
S-7
Green solid: m.p. 78-80 C; 1H NMR (400 MHz, CDCl3): 8.71 (d, J = 6.8 Hz, 1 H),
8.49-8.48 (m, 2 H), 8.19-8.14(m, 2 H), 7.76 (t, J = 6.8 Hz, 1 H), 7.27 (d, J = 8.4 Hz, 2
H), 7.05 (d, J = 8.4 Hz, 2 H), 6.98 (d, J = 8.4 Hz, 2 H), 6.73 (d, J = 8.4 Hz, 2 H), 3.81
(s, 3 H), 3.72 (s, 3 H);
13
(C), 142.7 (C), 138.8 (CH), 138.7 (C), 136.1 (CH), 132.7 (CH), 132.1 (2CH), 130.8
(2CH), 128.5 (CH), 128.1 (C), 127.0 (CH), 124.2 (CH), 121.6 (C), 115.6 (2CH),
113.9 (2CH), 55.4 (CH3), 55.2 (CH3); HRMS (FAB+) cal for C23H20O2N+ 342.1494,
found 342.1497; IR (KBr): 2923, 2854, 1604, 1511, 1465, 1442, 1396, 1249, 1180,
1056 ( B-F), 871, 794, 755 and 694 cm-1.
Green solid: m.p. 105-107 C; 1H NMR (400 MHz, CDCl3): 8.59 (d, J = 6.8 Hz, 1
H), 8.44-8.41 (m, 2 H), 8.16-8.10 (m, 2 H), 7.73 (t, J = 6.8 Hz, 1 H), 7.45-7.41 (m, 2
H), 7.15-7.12 (m, 4 H), 6.91-6.87 (m, 2 H); 13C NMR (100 MHz, CDCl3): 164.4 (d,
JC-F = 122.7 Hz, C), 161.9 (d, JC-F = 119.8 Hz, C), 143.1 (C), 142.8 (C), 138.4 (CH),
138.2 (C), 136.5 (CH), 133.1 (d, JC-F = 8.3 Hz, 2CH), 132.9 (CH), 132.0 (d, JC-F = 3.0
Hz, C), 131.4 (d, JC-F = 8.3 Hz, 2CH), 128.4 (CH), 127.3 (CH), 125.7 (d, JC-F = 3.8 Hz,
C), 124.3 (CH), 117.3 (d, JC-F = 22.0 Hz, 2CH), 115.6 (d, JC-F = 22.0 Hz, 2CH);
HRMS (FAB+) cal for C21H14F2N+ 318.1094, found 318.1098; IR (KBr): 3077, 2923,
2854, 1604, 1511, 1465, 1434, 1403, 1342, 1226, 1164, 1056 ( B-F), 825, 725 and 694
cm-1.
S-8
Yellow solid: m.p. 126-128 C; 1H NMR (400 MHz, CDCl3): 9.23 (d, J = 7.2 Hz, 1
H), 8.39 (d, J = 8.8 Hz, 1 H), 8.30 (d, J = 8.8 Hz, 1 H), 8.18 (t, J = 6.8 Hz, 1 H), 8.12
(td, J = 7.2, 1.2 Hz, 1 H), 8.07 (d, J = 8.8 Hz, 1 H), 3.38 (t, J = 8.4 Hz, 2 H), 2.89 (t, J
= 7.6 Hz, 2 H), 1.81-1.69 (m, 4 H), 1.16 (t, J = 7.2 Hz, 3 H), 1.04 (t, J = 7.2 Hz, 3
H);
13
C NMR (100 MHz, CDCl3): 145.2 (C), 142.4 (C), 138.6 (CH), 138.0 (C),
135.4 (CH), 132.2 (CH), 128.6 (CH), 125.8 (CH), 125.0 (CH), 35.4 (CH2), 30.1 (CH2),
23.7 (CH2), 19.7 (CH2), 13.9 (CH3), 13.8 (CH3); HRMS (FAB+) cal for C15H20N+
214.1596, found 214.1593; IR (KBr): 3085, 2962, 2923, 2877, 1735, 1643, 1619,
1442, 1403, 1342, 1288, 1056 ( B-F), 833 and 717 cm-1.
Yellow solid: m.p. 88-90 C; 1H NMR (400 MHz, CDCl3): 9.21 (d, J = 6.8 Hz, 1 H),
8.39-8.35 (m, 2 H), 8.26-8.19 (m, 2 H), 8.00 (t, J = 7.2 Hz, 1 H), 5.04 (s, 2 H), 4.76 (s,
2 H), 3.49 (s, 3 H), 3.45 (s, 3 H);
13
(C), 136.8 (CH), 136.7 (CH), 135.9 (C), 133.6 (CH), 128.2 (CH), 127.8 (CH), 124.8
(CH), 70.2 (CH2), 64.9 (CH2), 59.0 (CH3), 58.9 (CH3); HRMS (FAB+) cal for
C13H16O2N+ 218.1181, found 218.1181; IR (KBr): 3085, 2923, 2854, 1735, 1643,
1450, 1380, 1342, 1288, 1187, 1049 ( B-F), 956 and 871 cm-1.
S-9
Yellow solid: m.p. 193-195 C; 1H NMR (500 MHz, CD2Cl2): 8.79 (d, J = 5.6 Hz, 1
H), 8.59-8.52 (m, 3 H), 8.30 (t, J = 6.0 Hz, 1 H), 7.94-7.88 (m, 2 H), 7.51-7.48 (m, 2
H), 7.44-7.43 (m, 1 H), 7.39 (d, J = 3.2 Hz, 1 H), 7.09-7.08 (m, 1 H); 13C NMR (125
MHz, CD2Cl2): 143.0 (C), 137.5 (CH), 137.4 (CH), 136.6 (C), 134.9 (CH), 134.5
(C), 133.8 (CH), 133.6 (CH, C), 131.9 (CH, C), 131.5 (CH), 130.1 (CH), 128.8 (CH),
128.4 (CH), 128.2 (CH), 125.4 (CH); HRMS (FAB+) cal for C17H12S2N+ 294.0406,
found 294.0412; IR (KBr): 3108, 2923, 2854, 1612, 1589, 1519, 1442, 1396, 1357,
1326, 1056 ( B-F), 933 and 871 cm-1.
Yellow solid: m.p. 102-104 C; 1H NMR (400 MHz, CDCl3): 8.47-8.39 (m, 3 H),
8.20 (d, J = 8.8 Hz, 1 H), 8.17-8.12 (m, 1 H), 7.74 (td, J = 7.2, 1.6 Hz, 1 H), 7.71-7.65
(m, 3 H), 7.42-7.39 (m, 2 H), 2.29 (s, 3 H); 13C NMR (100 MHz, CDCl3): 143.2 (C),
142.1 (C), 139.5 (CH), 135.6 (CH), 135.1 (C), 132.3 (CH), 131.2 (CH), 130.7 (2CH),
129.8 (C), 129.0 (2CH), 128.1 (CH), 126.7 (CH), 124.0 (CH), 20.1 (CH3); HRMS
(FAB+) cal for C16H14N+ 220.1126, found 220.1125; IR (KBr): 3085, 2923, 2869,
1643, 1619, 1527, 1442, 1403, 1349, 1056 ( B-F), 825, 786 and 709 cm-1.
S-10
Yellow solid: m.p. 154-156 C; 1H NMR (400 MHz, CDCl3): 8.64-8.54 (m, 2 H),
8.38 (d, J = 6.8 Hz, 1 H), 8.25 (d, J = 8.8 Hz, 1 H), 8.19 (t, J = 8.0 Hz, 1 H), 7.77 (t, J
= 6.8 Hz, 1 H), 7.73-7.67 (m, 3 H), 7.45-7.42 (m, 2 H), 2.60 (q, J = 7.6 Hz, 2 H), 1.19
(t, J = 7.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3): 142.9 (C), 142.5 (C), 140.6 (C),
138.2 (CH), 135.9 (CH), 132.8 (CH), 131.4 (CH), 130.8 (2CH), 129.6 (C), 129.4
(2CH), 128.8 (CH), 127.9 (CH), 124.2 (CH), 26.7 (CH2), 14.6 (CH3); HRMS (FAB+)
cal for C17H16N+ 234.1277, found 234.1284; IR (KBr): 3070, 2923, 2854, 1643, 1619,
1589, 1442, 1403, 1334, 1218, 1056 ( B-F), 786 and 709 cm-1.
4-(Ethoxycarbonyl)-3-phenylquinolizin-5-ium tetrafluoroborate (3aj)
Yellow solid: m.p. 171-173 C; 1H NMR (400 MHz, CD3OD): 9.34 (dd, J = 6.8, 0.8
Hz, 1 H), 8.69-8.66 (m, 2 H), 8.51-8.46 (m, 1 H), 8.44 (d, J = 8.8 Hz, 1 H), 8.17-8.15
(m, 1 H), 7.62-7.55 (m, 5 H), 4.35 (q, J = 7.6 Hz, 2 H), 1.00 (t, J = 7.2 Hz, 3 H); 13C
NMR (100 MHz, CD3OD): 162.6 (C), 143.9 (C), 139.7 (CH), 139.1 (C), 138.9
(CH), 136.1 (C), 135.3 (CH, C), 131.2 (CH), 130.4 (2CH), 129.8 (3CH), 129.6 (CH),
126.7 (CH), 65.5 (CH2), 13.6 (CH3); HRMS (FAB+) cal for C18H16O2N+ 278.1176,
found 278.1180; IR (KBr): 2923, 2854, 1735, 1457, 1434, 1373, 1342, 1249, 1157,
1056 ( B-F), 817 and 755 cm-1.
S-11
Black oil; 1H NMR (400 MHz, CD3OD): 9.62 (d, J = 7.2 Hz, 1 H), 8.59 (dd, J = 8.4,
1.2 Hz, 1 H), 8.51 (d, J = 8.8 Hz, 1 H), 8.44-8.40 (m, 1 H), 8.30 (d, J = 8.4 Hz, 1 H),
8.16 (td, J = 7.2, 1.6 Hz, 1 H), 7.49 (d, J = 8.0 Hz, 2 H), 7.43 (d, J = 8.0 Hz, 2 H),
5.18 (s, 2 H), 2.46 (s, 3 H);
13
141.2 (C), 140.3 (C), 139.9 (CH), 137.9 (CH), 135.6 (CH), 134.5 (C), 130.8 (2CH),
130.6 (2CH), 129.4 (CH), 128.1 (CH), 125.6 (CH), 58.8 (CH2), 21.3 (CH3); HRMS
(FAB+) cal for C17H16ON+ 250.1232, found 250.1231; IR (KBr): 3525, 3262, 3124,
3077, 2923, 2869, 1643, 1619, 1511, 1442, 1403, 1342, 1288, 1218, 1187, 1064 ( B-F)
and 825cm-1.
Yellow solid: m.p. 166-168 C; 1H NMR (400 MHz, CDCl3): 8.46(dd, J = 6.8, 0.8
Hz, 1 H), 8.40 (d, J = 8.4 Hz, 1 H), 8.32 (s, 1 H), 8.05 (td, J = 6.8, 1.2 Hz, 1 H), 7.61
(td, J = 7.2, 1.6 Hz, 1 H), 7.45-7.37 (m, 5 H), 7.27-7.18 (m, 5 H), 7.03-6.95 (m, 5 H);
13
C NMR (100 MHz, CDCl3): 150.7 (C), 144.6 (C), 142.6 (C), 138.4 (C), 136.3 (C),
136.0 (CH), 134.5 (C), 132.5 (CH), 130.5 (2CH), 130.4 (CH), 130.3 (2CH), 129.6
(2CH), 129.5 (2CH), 128.8 (CH), 128.2 (CH, C), 128.1 (2CH), 127.7 (3CH), 126.9
(CH), 123.4 (CH); HRMS (FAB+) cal for C27H20N+ 358.1590, found 358.1597; IR
(KBr): 3062, 2923, 2854, 1643, 1612, 1581, 1496, 1442, 1411, 1349, 1326, 1272,
1195, 1149, 1056 ( B-F), 894, 840, 740 and 701cm-1.
S-12
Yellow solid: m.p. 250-252 C; 1H NMR (400 MHz, d6-DMSO): 9.14 (s, 1 H), 8.87
(d, J = 8.4 Hz, 1 H), 8.67 (d, J = 7.2 Hz, 1 H), 8.54 (t, J = 7.6 Hz, 1 H), 8.08 (t, J = 6.8
Hz, 1 H), 7.51-7.42 (m, 5 H), 7.27-7.20 (m, 3 H), 7.13-7.07 (m, 2 H), 3.64 (s, 3 H);
13
C NMR (100 MHz, d6-DMSO): 164.7 (C), 145.4 (C), 142.4 (C), 138.8 (C), 137.8
(CH), 134.9 (C), 134.6 (CH), 134.4 (C), 130.5 (CH), 130.4 (2CH), 130.1 (C), 129.3
(2CH), 129.2 (2CH), 128.5 (CH), 128.1 (CH), 127.7 (2CH), 126.5 (CH), 125.8 (CH),
53.2 (CH3); HRMS (FAB+) cal for C23H18O2N+ 340.1338, found 340.1336; IR (KBr):
3062, 1735, 1643, 1442, 1411, 1326, 1249, 1149, 1056 ( B-F), 825 and 786 cm-1.
2-Methyl-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3da)
Yellow solid: m.p. 88-90 C; 1H NMR (400 MHz, CDCl3): 8.43-8.37 (m, 3 H), 8.12
(t, J = 7.2 Hz, 1 H), 7.65 (td, J = 7.2, 1.2 Hz, 1 H), 7.40-7.36 (m, 3 H), 7.32-7.28 (m,
2 H), 7.23-7.18 (m, 3 H), 7.09-7.06 (m, 2 H), 2.37 (s, 3 H);
13
CDCl3): 149.9 (C), 143.7 (C), 142.6 (C), 140.2 (C), 135.8 (CH), 134.5 (C), 132.5
(CH), 130.5 (CH), 130.1 (2CH, C), 129.7 (2CH), 128.9 (2CH), 128.5 (2CH), 128.3
(CH), 127.7 (CH), 126.9 (CH), 123.0 (CH), 21.7 (CH3); HRMS (FAB+) cal for
C22H18N+ 296.1439, found 296.1438; IR (KBr): 3062, 2923, 2854, 1643, 1619, 1581,
1496, 1442, 1411, 1326, 1280, 1226, 1164, 1056 ( B-F), 887, 755 and 725 cm-1.
S-13
Yellow solid: m.p. 224-225 C; 1H NMR (400 MHz, CDCl3): 8.46 (d, J = 8.4 Hz, 1
H), 8.39-8.37 (m, 2 H), 8.14 (t, J = 7.6 Hz, 1 H), 7.66 (td, J = 7.2, 1.2 Hz, 1 H),
7.39-7.35 (m, 3 H), 7.29-7.27 (m, 2 H), 7.23-7.19 (m, 3 H), 7.09-7.07 (m, 2 H), 2.62 (t,
J = 7.6 Hz, 2 H), 1.70-1.59 (m, 2 H), 0.85 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz,
CDCl3): 153.6 (C), 143.9 (C), 142.8 (C), 140.1 (C), 135.9 (CH), 134.1 (C), 132.5
(CH), 130.4 (CH), 130.3 (C), 130.1 (2CH), 129.7 (2CH), 129.3 (2CH), 128.3 (3CH),
127.9 (CH), 125.9 (CH), 123.1 (CH), 35.9 (CH2), 22.4 (CH2), 13.8 (CH3); HRMS
(FAB+) cal for C24H22N+ 324.1752, found 324.1756; IR (KBr): 3062, 2962, 2923,
2869, 1643, 1619, 1581, 1450, 1411, 1342, 1280, 1164, 1056 ( B-F) and 856 cm-1.
2-Cyclohexyl-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3fa)
Green solid: m.p. 269-271 C; 1H NMR (400 MHz, CDCl3): 8.55 (d, J = 8.8 Hz, 1
H), 8.43 (s, 1 H), 8.36 (d, J = 7.2 Hz, 1 H)), 8.15 (t, J = 8.0 Hz, 1 H), 7.67 (t, J = 7.2
Hz, 1 H), 7.40-7.32 (m, 3 H), 7.28-7.25 (m, 2 H), 7.23-7.17 (m, 3 H), 7.07-7.05 (m, 2
H), 2.52-2.46 (m, 1 H), 1.84-1.79 (m, 2 H), 1.76-1.72 (m, 2 H), 1.63-1.53 (m, 2 H),
1.32-1.25 (m, 2 H), 1.06-0.97 (m, 2 H);
13
144.0 (C), 143.1 (C), 139.8 (C), 135.8 (CH), 134.1 (C), 132.3 (CH), 130.4 (CH),
130.0 (2CH), 129.7 (2CH), 129.4 (2CH), 128.3 (CH, C), 128.2 (3CH), 124.4 (CH),
123.2 (CH), 41.6 (CH), 33.3 (2CH2), 26.2 (2CH2), 25.4 (CH2); HRMS (FAB+) cal for
C27H26N+ 364.2060, found 364.2063; IR (KBr): 2923, 2854, 1743, 1681, 1643, 1619,
1519, 1450, 1411, 1342, 1164 , 1056 ( B-F) and 794 cm-1.
S-14
Yellow solid: m.p. 230-232 C; 1H NMR (400 MHz, CDCl3): 8.68 (d, J = 9.2 Hz, 1
H), 8.48 (s, 1 H), 7.91-7.87 (m, 2 H), 7.43-7.35 (m, 5 H), 7.21-7.14 (m, 5 H),
7.02-6.98 (m, 3 H), 6.96-6.89 (m, 2 H), 3.71 (s, 3 H); 13C NMR (100 MHz, CDCl3):
155.6 (C), 148.3 (C), 143.5 (C), 138.6 (C), 138.5 (C), 136.2 (C), 134.6 (C), 130.6 (C),
130.5 (CH), 130.4 (2CH), 130.1 (2CH), 129.8 (2CH), 129.7 (CH), 129.5 (2CH), 128.8
(CH), 128.5 (CH), 128.2 (2CH), 127.8 (3CH), 127.2 (CH), 115.9 (CH), 56.6 (CH3);
HRMS (FAB+) cal for C28H22ON+ 388.1696, found 388.1702; IR (KBr): 3062, 2923,
2854, 1619, 1511, 1427, 1357, 1280, 1234, 1195, 1149, 1056 ( B-F) and 833 cm-1.
2-(4-chlorophenyl)-7-methyl-3,4-diphenylquinolizin-5-ium tetrafluoroborate
(3ha)
Yellow solid: m.p. 189-191 C; 1H NMR (400 MHz, CDCl3): 8.34 (s, 1 H), 8.32 (d,
J = 8.8 Hz, 1 H), 8.19 (s, 1 H), 7.76 (d, J = 8.8 Hz, 1 H), 7.43-7.36 (m, 5 H), 7.22 (d, J
= 8.8 Hz, 2 H), 7.17 (d, J = 8.8 Hz, 2 H), 7.05-6.99 (m, 3 H), 6.98-6.94 (m, 2 H), 2.37
(s, 3 H); 13C NMR (100 MHz, CDCl3): 148.5 (C), 144.0 (C), 141.1 (C), 138.2 (CH),
138.1 (C), 134.9 (C), 134.8 (C), 134.6 (C), 134.4 (C), 130.9 (2CH, C), 130.4 (4CH),
130.3 (2CH), 129.6 (2CH), 128.3 (2CH), 127.7 (2CH), 127.6 (CH), 126.7 (2CH), 19.1
(CH3); HRMS (FAB+) cal for C28H21ClN+ 406.1363, found 406.1360; IR (KBr): 3062,
2923, 2854, 1619, 1496, 1427, 1349, 1272, 1195, 1149, 1056 ( B-F), 809, 740 and 624
cm-1.
S-15
Yellow solid: m.p. 254-256 C; 1H NMR (400 MHz, CDCl3): 8.58 (d, J = 7.2 Hz, 1
H), 8.33 (s, 1 H), 7.98 (d, J = 1.2 Hz, 1 H), 7.64 (dd, J = 7.2, 1.2 Hz, 1 H), 7.47-7.44
(m, 3 H), 7.36-7.33 (m, 2 H), 7.21-7.19 (m, 3 H), 7.14-7.11 (m, 2 H), 2.89 (s, 3 H),
2.73 (s, 3 H); 13C NMR (100 MHz, CDCl3): 150.0 (C), 142.4 (C), 141.3 (C), 138.3
(CH), 136.9 (C), 136.0 (C), 134.1 (C), 133.2 (CH), 130.8 (CH), 130.7 (2CH, C),
129.9 (2CH), 129.3 (2CH), 128.4 (CH), 128.3 (2CH), 126.0 (CH), 123.9 (CH), 21.8
(CH3), 19.3 (CH3); HRMS (FAB+) cal for C23H20N+ 310.1596, found 310.1595; IR
(KBr): 3062, 2923, 2854, 1643, 1619, 1496, 1442, 1388, 1365, 1280, 1195, 1056 (
B-F),
Yellow solid: m.p. 128-130 C; 1H NMR (400 MHz, CDCl3): 8.71 (d, J = 7.6 Hz, 1
H), 8.23 (d, J = 8.4 Hz, 1 H), 8.07-8.03 (m, 2 H), 7.70 (td, J = 6.8, 1.2 Hz, 1 H),
7.63-7.59 (m, 2 H), 7.53-7.50 (m, 3 H), 7.49-7.43 (m, 5 H), 7.21-7.14 (m, 5 H);
13
NMR (100 MHz, CDCl3): 143.1 (C), 142.4 (C), 139.3 (C), 138.6 (CH), 138.1 (C),
136.0 (CH), 135.9 (C), 134.6 (C), 133.8 (CH), 130.8 (CH), 130.7 (2CH), 129.9 (C),
129.8 (4CH), 129.7 (CH), 129.4 (2CH), 129.2 (2CH), 128.4 (CH), 128.3 (2CH), 126.2
(CH), 123.8 (CH); HRMS (FAB+) cal for C27H20N+ 358.1596, found 358.1595; IR
(KBr): 3062, 2923, 1635, 1596, 1496, 1434, 1388, 1272, 1226, 1157, 1056 ( B-F), 840,
678 and 624 cm-1.
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Yellow solid: m.p. 278-280 C; 1H NMR (400 MHz, CDCl3): 8.58 (d, J = 8.8 Hz, 1
H), 8.38 (s, 1 H), 8.21 (d, J = 8.8 Hz, 1 H), 8.06 (d, J = 5.6 Hz, 1 H), 7.46-7.37 (m, 5
H), 7.29-7.25 (m, 3 H), 7.23-7.19 (m, 3 H), 2.47 (s, 3 H);
13
CDCl3): 142.9 (C), 140.3 (CH), 138.9 (C), 138.1 (C), 136.1 (CH), 134.4 (C), 134.2
(C), 134.1 (C), 134.0 (C), 132.7 (CH), 131.1 (2CH), 130.6 (CH), 130.2 (C), 129.8
(2CH), 129.5 (2CH), 128.7 (CH), 128.5 (2CH), 125.6 (CH), 123.6 (CH), 19.2 (CH3);
HRMS (FAB+) cal for C24H18SN+ 352.1160, found 352.1158; IR (KBr): 3116, 3062,
2923, 1596, 1511, 1465, 1442, 1357, 1326, 1218, 1056 ( B-F), 856, 655 and 624 cm-1.
8-Methyl-4,5-diphenylfuro[2,3-a]quinolizin-6-ium tetrafluoroborate (3la)
Yellow solid: m.p. 264-266 C; 1H NMR (400 MHz, CDCl3): 8.67 (d, J = 8.8 Hz, 1
H), 8.37 (s, 1 H), 8.19 (t, J = 2.0 Hz, 1 H), 8.15 (d, J = 8.8 Hz, 1 H), 7.46-7.40 (m, 5
H), 7.27-7.20 (m, 5 H), 6.86 (t, J = 2.0 Hz, 1 H), 2.45 (s, 3 H); 13C NMR (100 MHz,
CDCl3): 152.1 (CH), 145.6 (C), 139.2 (CH), 138.6 (C), 133.7 (C), 133.6 (C), 132.8
(C), 131.8 (C), 131.6 (CH), 131.3 (2CH), 131.2 (C), 130.7 (CH), 130.1 (C), 129.9
(2CH), 129.5 (2CH), 128.7 (CH), 128.5 (2CH), 119.9 (CH), 108.5 (CH), 19.3 (CH3);
HRMS (FAB+) cal for C24H18NO+ 336.1383, found 336.1389; IR (KBr): 3139, 3062,
2923, 1658, 1619, 1535, 1496, 1442, 1388, 1288, 1226, 1195, 1056 (
cm-1.
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B-F)
and 786
Yellow solid: m.p. 200-202 C; 1H NMR (400 MHz, CDCl3): 8.57 (d, J = 8.8 Hz, 1
H), 8.40-8.33 (m, 2 H), 8.18 (d, J = 8.8 Hz, 1 H), 8.03 (dd, J = 8.0, 1.6 Hz, 1 H), 7.70
(d, J = 9.2 Hz, 1 H), 7.61 (t, J = 7.6 Hz, 1 H), 7.36-7.18 (m, 7 H), 7.13-7.11 (m, 2 H),
7.05-7.03 (m, 2 H); 13C NMR (100 MHz, CDCl3): 148.2 (C), 145.7 (C), 142.8 (CH),
140.8 (C), 137.6 (CH), 135.8 (C), 135.3 (C), 134.7 (C), 130.3 (CH), 130.2 (2CH),
129.8 (CH), 129.6 (CH), 129.5 (2CH), 129.4 (2CH), 129.3 (C), 129.0 (CH), 128.5
(2CH), 128.4 (CH), 127.8 (CH), 125.4 (CH), 123.8 (CH); HRMS (FAB+) cal for
C25H18N+ 332.1434, found 332.1440; IR (KBr): 3201, 2923, 2854, 1619, 1573, 1504,
1427, 1365, 1311, 1187, 1141, 1056 ( B-F), 794, 771, 740 and 694 cm-1.
6,7-Diphenyl-1,2,3,4-tetrahydroquinolizin-5-ium tetrafluoroborate (3aa)
Yellow liquid; 1H NMR (400 MHz, CDCl3): 8.16 (d, J = 8.4 Hz, 1 H), 7.83 (d, J =
8.4 Hz, 1 H), 7.38-7.32 (m, 5 H), 7.18-7.12 (m, 3 H), 7.05-7.03 (m, 2 H), 4.25 (t, J =
6.4 Hz, 2 H), 3.38 (t, J = 6.4 Hz, 2 H), 2.05-1.98 (m, 4 H);
13
CDCl3): 156.5 (C), 153.5 (C), 144.6 (CH), 139.9 (C), 135.6 (C), 130.8 (C), 130.3
(CH), 129.7 (2CH), 129.2 (2CH), 128.9 (2CH), 128.3 (CH), 128.2 (2CH), 127.6 (CH),
53.6 (CH2), 29.3 (CH2), 21.4 (CH2), 16.9 (CH2); HRMS (FAB+) cal for C21H20N+
286.1590, found 286.1595; IR (KBr): 3062, 2954, 1612, 1581, 1481, 1450, 1403,
1349, 1265, 1164, 1056 ( B-F), 856, 655 and 624 cm-1.
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NOE data.
Irradiation
Intensity increase
H1 ( 9.62)
H2 ( 8.16, 2.47 %)
H3 ( 5.18)
H3 ( 5.18, 4.79 %)
H1 ( 9.62, 3.97 %)
H7 ( 7.49, 0.63 %)
H4 ( 8.51)
H5 ( 8.59)
H6 ( 8.30)
H5 ( 8.59, 1.79 %)
H4 ( 8.51, 1.86 %)
H7 ( 7.49, 1.32 %)
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References
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Table 1.
Identification code
121229lt_0m
Empirical formula
C16 H14 B F4 N
Formula weight
307.09
Temperature
100(2) K
Wavelength
0.71073
Crystal system
Monoclinic
Space group
Unit cell dimensions
P 2(1)/c
a = 9.2845(6)
= 90.
b = 8.1916(5)
= 102.541(3).
c = 19.3256(12)
= 90.
Volume
1434.74(16) 3
Density (calculated)
1.422 Mg/m3
Absorption coefficient
0.118 mm-1
F(000)
632
Crystal size
2.16 to 28.34.
Index ranges
Reflections collected
13349
Independent reflections
99.5 %
Absorption correction
Refinement method
Full-matrix least-squares on F2
3556 / 0 / 199
Goodness-of-fit on F2
1.103
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Table 1.
Identification code
121217lt_0m
Empirical formula
C34 H32 B2 F8 N2
Formula weight
642.24
Temperature
100(2) K
Wavelength
0.71073
Crystal system
Triclinic
Space group
P-1
a = 7.2675(3)
= 82.921(2).
b = 7.9484(4)
= 83.610(2).
c = 27.5441(13)
= 74.824(2).
Volume
1518.70(12) 3
Density (calculated)
1.404 Mg/m3
Absorption coefficient
0.115 mm-1
F(000)
664
Crystal size
0.75 to 28.34.
Index ranges
Reflections collected
24864
Independent reflections
98.3 %
Absorption correction
Refinement method
Full-matrix least-squares on F2
7473 / 0 / 417
Goodness-of-fit on F2
1.090
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Table 1.
Identification code
130111lt_0m
Empirical formula
C36 H32 B2 F8 N2 O4
Formula weight
730.26
Temperature
100(2) K
Wavelength
0.71073
Crystal system
triclinic
Space group
P -1
a = 10.5920(2)
= 89.8660(10).
b = 11.1165(2)
= 69.4220(10).
c = 14.8645(3)
= 88.0730(10).
Volume
1637.55(5) 3
Density (calculated)
1.481 Mg/m3
Absorption coefficient
0.126 mm-1
F(000)
752
Crystal size
1.46 to 28.36.
Index ranges
Reflections collected
29457
Independent reflections
99.0 %
Absorption correction
Refinement method
Full-matrix least-squares on F2
8105 / 0 / 483
Goodness-of-fit on F2
1.103
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11
19
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