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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

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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

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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

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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

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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.


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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

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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

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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.

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

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.

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.

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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.

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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.

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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.

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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.

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

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

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.

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

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

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),

840 and 732 cm-1.

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

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

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

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)

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

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

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

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.

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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

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.

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H and 13C NMR spectra of compound 3aa.

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H and 13C NMR spectra of compound 3ab.

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H and 13C NMR spectra of compound 3ac.

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H and 13C NMR spectra of compound 3ad.

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H and 13C NMR spectra of compound 3ae.

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H and 13C NMR spectra of compound 3af.

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H and 13C NMR spectra of compound 3ag.

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H and 13C NMR spectra of compound 3ah.

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H and 13C NMR spectra of compound 3ai.

H and 13C NMR spectra of compound 3aj.


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Electronic Supplementary Material (ESI) for Chemical Communications


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H and 13C NMR spectra of compound 3ak.


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Electronic Supplementary Material (ESI) for Chemical Communications


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H and 13C NMR spectra of compound 3ba.


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H and 13C NMR spectra of compound 3ca.


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H and 13C NMR spectra of compound 3da.


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H and 13C NMR spectra of compound 3ea.


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H and 13C NMR spectra of compound 3fa.


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H and 13C NMR spectra of compound 3ga.


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H and 13C NMR spectra of compound 3ha.


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H and 13C NMR spectra of compound 3ia.


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H and 13C NMR spectra of compound 3ja.


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H and 13C NMR spectra of compound 3ka.


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H and 13C NMR spectra of compound 3la.


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H and 13C NMR spectra of compound 3ma.


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H and 13C NMR spectra of compound 3aa.

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ORTEP diagram of compound 3ah.

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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

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ORTEP diagram of compound 3ai.

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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

Unit cell dimensions

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

0.20 x 0.20 x 0.12 mm3

Theta range for data collection

0.75 to 28.34.

Index ranges

-9<=h<=7, -9<=k<=10, -35<=l<=36

Reflections collected

24864

Independent reflections

7473 [R(int) = 0.0291]

Completeness to theta = 28.34

98.3 %

Absorption correction

Semi-empirical from equivalents

Max. and min. transmission

0.9422 and 0.8867

Refinement method

Full-matrix least-squares on F2

Data / restraints / parameters

7473 / 0 / 417

Goodness-of-fit on F2

1.090

Final R indices [I>2sigma(I)]

R1 = 0.0443, wR2 = 0.1210

R indices (all data)

R1 = 0.0708, wR2 = 0.1471

Largest diff. peak and hole

0.334 and -0.352 e.-3

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ORTEP diagram of compound 3aj.

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This journal is The Royal Society of Chemistry 2013

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

Unit cell dimensions

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

0.3 x 0.27 x 0.22 mm3

Theta range for data collection

1.46 to 28.36.

Index ranges

-14<=h<=10, -14<=k<=14, -19<=l<=16

Reflections collected

29457

Independent reflections

8105 [R(int) = 0.0356]

Completeness to theta = 28.36

99.0 %

Absorption correction

Semi-empirical from equivalents

Max. and min. transmission

0.9486 and 0.8900

Refinement method

Full-matrix least-squares on F2

Data / restraints / parameters

8105 / 0 / 483

Goodness-of-fit on F2

1.103

Final R indices [I>2sigma(I)]

R1 = 0.0514, wR2 = 0.1578

R indices (all data)

R1 = 0.0783, wR2 = 0.1990

Largest diff. peak and hole

0.791 and -0.656 e.-3

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11

B NMR spectra of compound 3aa.

19

F NMR spectra of compound 3aa.

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