Quinolizinium Salts Chemcom SI

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is The Royal Society of Chemistry 2013
A convenient synthesis of quinolizinium salts through Rh(III) or

Ru(II)-catalyzed C-H bond activation of 2-alkenylpyridine
Ching-Zong Luo, Parthasarathy Gandeepan and ChienHong Cheng*

Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan
chcheng@mx.nthu.edu.tw
Supporting Information
Table of contents
Page No
General Procedure for the Synthesis of Quinolizinium Salts (Condition A) S-2

Table 1. Optimization Studies for Rh(III)-Catalyzed Quinolizinium Salt
S-3
Formation
General Procedure for the Synthesis of Quinolizinium Salts (Condition B) S-4
Table 2. Optimization Studies for Ru(II)-Catalyzed Quinolizinium Salt
S-5
Formation
Synthesis of Tetrahydroquinolizinium Salt 3aa
S-6
S-7
H, 13C, HRMS and IR Data
NOE Data of Compounds 3ak
S-19
References
S-20
S-21
H and 13C NMR Spectra
ORTEP Diagram and X-ray Data of 3ah, 3ai and 3aj
S-45
11
S-51
B NMR Spectrum of Compound 3aa
19
S-51
F NMR Spectrum of Compound 3aa
S-1

General. All reactions were conducted under an oxygen atmosphere (condition A) or

a nitrogen atmosphere (condition B) on a dual-manifold schlenk line unless otherwise
mentioned and in oven-dried glass wares. All solvents were dried according to known
methods and distilled prior to use.1 [Cp*RhCl2]2 was prepared from RhCl3.xH2O
following a literature procedure.2 Other reagents were commercially available and
used as purchased.
General Procedure for the Synthesis of Quinolizinium Salts (Condition A).
A sealed tube containing [Cp*RhCl2]2 (1.8 mg, 0.0028 mmol) and

Cu(BF4)2.6H2O (49.0 mg, 0.14 mmol) was evacuated and purged with oxygen gas
three times. Then, 2-vinylpyridine 1 (0.28 mmol) and alkyne 2 (0.34 mmol) in MeOH
(1.0 mL) were added to the system via syringe under an oxygen atmosphere and the
reaction was allowed to stir at 60 C for 18 h under O2. When the reaction was
completed, the mixture was diluted with CH2Cl2 (10 mL) and filtered through a Celite
pad and the Celite pad was washed several times with CH2Cl2 (50 mL). The combined
filtrate was concentrated in vacuo and the residue was purified by column
chromatography on a silica gel column using DCM/MeOH (95:5) as eluent to afford
the desired pure product 3.
S-2

Table 1. Optimization Studies for Rh(III)-Catalyzed Quinolizinium Salt

Formationa
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

General Procedure for the Synthesis of Quinolizinium Salts (Condition B).
A sealed tube containing [RuCl2(p-cymene)]2 (3.5 mg, 0.0056 mmol), AgBF4

(6.0 mg, 0.028 mmol), and Cu(BF4)2.6H2O (197.0 mg, 0.56 mmol) was evacuated and
purged with nitrogen gas three times. Then, 2-vinylpyridine 1 (0.28 mmol) and alkyne
2 (0.34 mmol) in EtOAc (2.0 mL) were added to the system via syringe under a
nitrogen atmosphere and the reaction was allowed to stir at 100 C for 24 h. When the
reaction was completed, the mixture was diluted with CH2Cl2 (10 mL) and filtered
through a Celite pad and the Celite pad was washed several times with CH2Cl2 (50
mL). The combined filtrate was concentrated in vacuo and the residue was purified by
column chromatography on a silica gel column using DCM/MeOH (95:5) as eluent to
afford the desired pure product 3.
S-4

Table 2. Optimization Studies for Ru(II)-Catalyzed Quinolizinium Salt

Formationa
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,
0.14 mmol) under 1 atm. O2.

S-5

Synthesis of Tetrahydroquinolizinium Salt 3aa
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

3,4-Diphenylquinolizin-5-ium tetrafluoroborate (3aa)
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.
3,4-Di-p-tolylquinolizin-5-ium tetrafluoroborate (3ab)
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

3,4-Bis(4-methoxyphenyl)quinolizin-5-ium tetrafluoroborate (3ac)
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 NMR (100 MHz, CDCl3): 161.2 (C), 159.6 (C), 143.4
(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.
3,4-Bis(4-fluorophenyl)quinolizin-5-ium tetrafluoroborate (3ad)
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

3,4-Dipropylquinolizin-5-ium tetrafluoroborate (3ae)
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.
3,4-Bis(methoxymethyl)quinolizin-5-ium tetrafluoroborate (3af)
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 NMR (100 MHz, CDCl3): 142.8 (C), 139.6
(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

3,4-Di(thiophen-2-yl)quinolizin-5-ium tetrafluoroborate (3ag)
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.
3-Methyl-4-phenylquinolizin-5-ium tetrafluoroborate (3ah)
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

3-Ethyl-4-phenylquinolizin-5-ium tetrafluoroborate (3ai)
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

4-(Hydroxymethyl)-3-(p-tolyl)quinolizin-5-ium tetrafluoroborate (3ak)
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
C NMR (100 MHz, CD3OD): 144.6 (C), 143.2 (C),
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.
2,3,4-Triphenylquinolizin-5-ium tetrafluoroborate (3ba)
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

2-(Methoxycarbonyl)-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3ca)
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
C NMR (100 MHz,
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

3,4-Diphenyl-2-propylquinolizin-5-ium tetrafluoroborate (3ea)
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
C NMR (100 MHz, CDCl3): 158.4 (C),
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

7-Methoxy-2,3,4-triphenylquinolizin-5-ium tetrafluoroborate (3ga)
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

1,8-Dimethyl-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3ia)
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),
840 and 732 cm-1.
1,3,4-Triphenylquinolizin-5-ium tetrafluoroborate (3ja)
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.
S-16

8-Methyl-4,5-diphenylthieno[2,3-a]quinolizin-6-ium tetrafluoroborate (3ka)
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
C NMR (100 MHz,
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)
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.
S-17
B-F)
and 786

1,2-Diphenylpyrido[1,2-a]quinolin-11-ium tetrafluoroborate (3ma)
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
C NMR (100 MHz,
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.
S-18

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 %)
S-19

References
1. D. D. Perrin, W. L. F. Armarego, In Purification of Laboratory Chemicals, 3rd ed.;

Pergamon Press: New York, 1988.
2. C. White, A. Yates, P. M. Maitlis, Inorg. Synth. 1992, 29, 228.
S-20

H and 13C NMR spectra of compound 3aa.
S-21

H and 13C NMR spectra of compound 3ab.
S-22

H and 13C NMR spectra of compound 3ac.
S-23

H and 13C NMR spectra of compound 3ad.
S-24

H and 13C NMR spectra of compound 3ae.
S-25

H and 13C NMR spectra of compound 3af.
S-26

H and 13C NMR spectra of compound 3ag.
S-27

H and 13C NMR spectra of compound 3ah.
S-28

H and 13C NMR spectra of compound 3ai.
H and 13C NMR spectra of compound 3aj.

S-29

H and 13C NMR spectra of compound 3ak.

S-30

H and 13C NMR spectra of compound 3ba.

S-31

H and 13C NMR spectra of compound 3ca.

S-32

H and 13C NMR spectra of compound 3da.

S-33

H and 13C NMR spectra of compound 3ea.

S-34

H and 13C NMR spectra of compound 3fa.

S-35

H and 13C NMR spectra of compound 3ga.

S-36

H and 13C NMR spectra of compound 3ha.

S-37

H and 13C NMR spectra of compound 3ia.

S-38

H and 13C NMR spectra of compound 3ja.

S-39

H and 13C NMR spectra of compound 3ka.

S-40

H and 13C NMR spectra of compound 3la.

S-41

H and 13C NMR spectra of compound 3ma.

S-42

S-43

H and 13C NMR spectra of compound 3aa.
S-44

ORTEP diagram of compound 3ah.
S-45

Table 1.
Crystal data and structure refinement for 3ah.
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
0.27 x 0.25 x 0.20 mm3
Theta range for data collection
2.16 to 28.34.
Index ranges
-12<=h<=12, -10<=k<=10, -23<=l<=25
Reflections collected
13349
Independent reflections
3556 [R(int) = 0.0252]
Completeness to theta = 28.34
99.5 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.9486 and 0.8851
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
3556 / 0 / 199
Goodness-of-fit on F2
1.103
Final R indices [I>2sigma(I)]
R1 = 0.0506, wR2 = 0.1587
R indices (all data)
R1 = 0.0661, wR2 = 0.1863
Largest diff. peak and hole
0.630 and -0.420 e.-3
S-46

ORTEP diagram of compound 3ai.
S-47

Table 1.
Crystal data and structure refinement for 3ai.
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
1.404 Mg/m3
0.115 mm-1
F(000)
664
Crystal size
0.20 x 0.20 x 0.12 mm3
0.75 to 28.34.
Index ranges
-9<=h<=7, -9<=k<=10, -35<=l<=36
24864
7473 [R(int) = 0.0291]
98.3 %
0.9422 and 0.8867
Refinement method
7473 / 0 / 417
1.090
R1 = 0.0443, wR2 = 0.1210
R1 = 0.0708, wR2 = 0.1471
0.334 and -0.352 e.-3
S-48

ORTEP diagram of compound 3aj.
S-49

Table 1.
Crystal data and structure refinement for 3aj.
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
1.481 Mg/m3
0.126 mm-1
F(000)
752
Crystal size
0.3 x 0.27 x 0.22 mm3
1.46 to 28.36.
Index ranges
-14<=h<=10, -14<=k<=14, -19<=l<=16
29457
8105 [R(int) = 0.0356]
99.0 %
0.9486 and 0.8900
Refinement method
8105 / 0 / 483
1.103
R1 = 0.0514, wR2 = 0.1578
R1 = 0.0783, wR2 = 0.1990
0.791 and -0.656 e.-3
S-50

11
B NMR spectra of compound 3aa.
19
F NMR spectra of compound 3aa.
S-51

Quinolizinium Salts Chemcom SI

Caricato da

Informazioni sul documento

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Quinolizinium Salts Chemcom SI

Caricato da

Copyright:

Formati disponibili

Electronic Supplementary Material (ESI) for Chemical Communications

This journal is The Royal Society of Chemistry 2013

A convenient synthesis of quinolizinium salts through Rh(III) or

Ching-Zong Luo, Parthasarathy Gandeepan and ChienHong Cheng*

General Procedure for the Synthesis of Quinolizinium Salts (Condition A) S-2

H, 13C, HRMS and IR Data

NOE Data of Compounds 3ak

H and 13C NMR Spectra

ORTEP Diagram and X-ray Data of 3ah, 3ai and 3aj

B NMR Spectrum of Compound 3aa

F NMR Spectrum of Compound 3aa

Electronic Supplementary Material (ESI) for Chemical Communications

General. All reactions were conducted under an oxygen atmosphere (condition A) or

A sealed tube containing [Cp*RhCl2]2 (1.8 mg, 0.0028 mmol) and

Electronic Supplementary Material (ESI) for Chemical Communications

Table 1. Optimization Studies for Rh(III)-Catalyzed Quinolizinium Salt

Electronic Supplementary Material (ESI) for Chemical Communications

General Procedure for the Synthesis of Quinolizinium Salts (Condition B).

A sealed tube containing [RuCl2(p-cymene)]2 (3.5 mg, 0.0056 mmol), AgBF4

Electronic Supplementary Material (ESI) for Chemical Communications

Table 2. Optimization Studies for Ru(II)-Catalyzed Quinolizinium Salt

0.14 mmol) under 1 atm. O2.

Electronic Supplementary Material (ESI) for Chemical Communications

Synthesis of Tetrahydroquinolizinium Salt 3aa

Electronic Supplementary Material (ESI) for Chemical Communications

3,4-Diphenylquinolizin-5-ium tetrafluoroborate (3aa)

3,4-Di-p-tolylquinolizin-5-ium tetrafluoroborate (3ab)

Electronic Supplementary Material (ESI) for Chemical Communications

3,4-Bis(4-methoxyphenyl)quinolizin-5-ium tetrafluoroborate (3ac)

C NMR (100 MHz, CDCl3): 161.2 (C), 159.6 (C), 143.4

3,4-Bis(4-fluorophenyl)quinolizin-5-ium tetrafluoroborate (3ad)

Electronic Supplementary Material (ESI) for Chemical Communications

3,4-Dipropylquinolizin-5-ium tetrafluoroborate (3ae)

3,4-Bis(methoxymethyl)quinolizin-5-ium tetrafluoroborate (3af)

C NMR (100 MHz, CDCl3): 142.8 (C), 139.6

Electronic Supplementary Material (ESI) for Chemical Communications

3,4-Di(thiophen-2-yl)quinolizin-5-ium tetrafluoroborate (3ag)

3-Methyl-4-phenylquinolizin-5-ium tetrafluoroborate (3ah)

Electronic Supplementary Material (ESI) for Chemical Communications

3-Ethyl-4-phenylquinolizin-5-ium tetrafluoroborate (3ai)

Electronic Supplementary Material (ESI) for Chemical Communications

4-(Hydroxymethyl)-3-(p-tolyl)quinolizin-5-ium tetrafluoroborate (3ak)

C NMR (100 MHz, CD3OD): 144.6 (C), 143.2 (C),

2,3,4-Triphenylquinolizin-5-ium tetrafluoroborate (3ba)

Electronic Supplementary Material (ESI) for Chemical Communications

2-(Methoxycarbonyl)-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3ca)

C NMR (100 MHz,

Electronic Supplementary Material (ESI) for Chemical Communications

3,4-Diphenyl-2-propylquinolizin-5-ium tetrafluoroborate (3ea)

C NMR (100 MHz, CDCl3): 158.4 (C),

Electronic Supplementary Material (ESI) for Chemical Communications

7-Methoxy-2,3,4-triphenylquinolizin-5-ium tetrafluoroborate (3ga)

Electronic Supplementary Material (ESI) for Chemical Communications

1,8-Dimethyl-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3ia)

840 and 732 cm-1.

1,3,4-Triphenylquinolizin-5-ium tetrafluoroborate (3ja)

Electronic Supplementary Material (ESI) for Chemical Communications

8-Methyl-4,5-diphenylthieno[2,3-a]quinolizin-6-ium tetrafluoroborate (3ka)

C NMR (100 MHz,

Electronic Supplementary Material (ESI) for Chemical Communications

1,2-Diphenylpyrido[1,2-a]quinolin-11-ium tetrafluoroborate (3ma)

C NMR (100 MHz,

Electronic Supplementary Material (ESI) for Chemical Communications

Electronic Supplementary Material (ESI) for Chemical Communications