a convenient synthesis of quinolizinium salts through rh ... · s-1 a convenient synthesis of...

S-1

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 Chien–Hong Cheng*

Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan

[email protected]

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

Formation S-3

General Procedure for the Synthesis of Quinolizinium Salts (Condition B) S-4

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

Formation S-5

Synthesis of Tetrahydroquinolizinium Salt 3aa’ S-6

1H,

13C, HRMS and IR Data S-7

NOE Data of Compounds 3ak’ S-19

References S-20

1H and

13C NMR Spectra S-21

ORTEP Diagram and X-ray Data of 3ah, 3ai and 3aj S-45

11B NMR Spectrum of Compound 3aa S-51

19F NMR Spectrum of Compound 3aa S-51

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

mailto:[email protected]

S-2

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-3

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

Formationa

Entry Solvent T ℃ Time (h) Yield (%)b

1 DME 30 24 10

2 t-amylOH 30 24 trace

3 DCE 30 24 20

4 MeOH 30 24 14

5 MeCN 30 24 -

6 THF 30 24 6

7 1,4-dioxane 30 24 -

8 DMF 30 24 trace

9 IPA 30 24 7

10 EtOAc 30 24 3

11 toluene 30 24 trace

12 CHCl3 30 24 12

13 PhCl 30 24 -

14 DCE 60 24 34

15 DCE 80 24 36

16 MeOH 60 24 54

17 MeOH 60 24 98c

18 MeOH 60 18 98c

19 MeOH 60 12 80c

aAll 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-4

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.


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

Formationa

Entry Solvent Time (h) Yield (%)b

1 t-amylOH 18 10

2 EtOH 18 5

3 tert-Butanol 18 30

4 DME 18 10

5 acetone 18 53

6 MeCN 18 -

7 toluene 18 -

8 THF 18 12

9 DCE 18 6

10 2-ethoxyethanol 18 22

11 1,4-dioxane 18 trace

12 DMF 18 trace

13 MeNO2 18 -

14

EtOAc 18 85

15 IPA 18 20

16 DMA 18 trace

17 DMSO 18 37

18 EtOAc 18 37c

19 EtOAc 18 25d

20 EtOAc 24 99e

21 t-amylOH 18 tracef

aAll 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.

eThe 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-6

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-7

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

Yellow solid: m.p. 175-177 °C;

1H NMR (400 MHz, CDCl3): δ 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); 13

C NMR (100

MHz, CDCl3): δ 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); 11

B NMR (160 MHz, CDCl3): δ -1.28;

19F NMR (470 MHz, CDCl3): δ -154.03, -154.08 and secondary isotopic shift (

10B,

11B) 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 (ν 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): δ 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

C

NMR (100 MHz, CDCl3): δ 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 (ν B-F) and

833 cm-1

.


S-8

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

Green solid: m.p. 78-80 °C; 1H NMR (400 MHz, CDCl3): δ 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): δ 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 (ν B-F), 871, 794, 755 and 694 cm-1

.

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



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); 13

C NMR (100 MHz, CDCl3): δ 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 (ν B-F), 825, 725 and 694

cm-1

.


S-9

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

Yellow solid: m.p. 126-128 °C; 1H NMR (400 MHz, CDCl3): δ 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): δ 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 (ν 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): δ 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): δ 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 (ν B-F), 956 and 871 cm-1

.


S-10

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

Yellow solid: m.p. 193-195 °C; 1H NMR (500 MHz, CD2Cl2): δ 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); 13

C NMR (125

MHz, CD2Cl2): δ 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 (ν 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): δ 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); 13

C NMR (100 MHz, CDCl3): δ 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 (ν B-F), 825, 786 and 709 cm-1

.


S-11

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

Yellow solid: m.p. 154-156 °C; 1H NMR (400 MHz, CDCl3): δ 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); 13

C NMR (100 MHz, CDCl3): δ 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 (ν B-F), 786 and 709 cm-1

.

4-(Ethoxycarbonyl)-3-phenylquinolizin-5-ium tetrafluoroborate (3aj)


1H NMR (400 MHz, CD3OD): δ 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); 13

C

NMR (100 MHz, CD3OD): δ 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 (ν B-F), 817 and 755 cm-1

.


S-12

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

Black oil;

1H NMR (400 MHz, CD3OD): δ 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): δ 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 (ν 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): δ 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);

13C NMR (100 MHz, CDCl3): δ 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 (ν B-F), 894, 840, 740 and 701cm-1

.


S-13

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


1H NMR (400 MHz, d

6-DMSO): δ 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);

13C NMR (100 MHz, d

6-DMSO): δ 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 (ν B-F), 825 and 786 cm-1

.

2-Methyl-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3da)


1H NMR (400 MHz, CDCl3): δ 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): δ 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 (ν B-F), 887, 755 and 725 cm-1

.


S-14

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); 13

C NMR (100 MHz,

CDCl3): δ 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 (ν B-F) and 856 cm-1

.

2-Cyclohexyl-3,4-diphenylquinolizin-5-ium tetrafluoroborate (3fa)



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): δ 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 (ν B-F) and 794 cm-1

.


S-15

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); 13

C NMR (100 MHz, CDCl3): δ

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 (ν 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): δ 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); 13

C NMR (100 MHz, CDCl3): δ 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 (ν B-F), 809, 740 and 624

cm-1

.


S-16

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); 13

C NMR (100 MHz, CDCl3): δ 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 (ν

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

C

NMR (100 MHz, CDCl3): δ 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 (ν B-F), 840,

678 and 624 cm-1

.


S-17

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): δ 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 (ν 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); 13

C NMR (100 MHz,

CDCl3): δ 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 (ν B-F) and 786

cm-1

.


S-18

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); 13

C NMR (100 MHz, CDCl3): δ 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 (ν 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): δ 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): δ 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 (ν B-F), 856, 655 and 624 cm-1

.


S-19

NOE data.

Irradiation Intensity increase

H1 (δ 9.62) H2 (δ 8.16, 2.47 %)

H3 (δ 5.18, 4.79 %)

H3 (δ 5.18) H1 (δ 9.62, 3.97 %)

H7 (δ 7.49, 0.63 %)

H4 (δ 8.51) H5 (δ 8.59, 1.79 %)

H5 (δ 8.59) H4 (δ 8.51, 1.86 %)

H6 (δ 8.30) H7 (δ 7.49, 1.32 %)


S-20

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-21

1H and

13C NMR spectra of compound 3aa.


S-22

1H and

13C NMR spectra of compound 3ab.


S-23

1H and

13C NMR spectra of compound 3ac.


S-24

1H and

13C NMR spectra of compound 3ad.


S-25

1H and

13C NMR spectra of compound 3ae.


S-26

1H and

13C NMR spectra of compound 3af.


S-27

1H and

13C NMR spectra of compound 3ag.


S-28

1H and

13C NMR spectra of compound 3ah.


S-29

1H and

13C NMR spectra of compound 3ai.

1H and

13C NMR spectra of compound 3aj.


S-30

1H and

13C NMR spectra of compound 3ak’.


S-31

1H and

13C NMR spectra of compound 3ba.


S-32

1H and

13C NMR spectra of compound 3ca.


S-33

1H and

13C NMR spectra of compound 3da.


S-34

1H and

13C NMR spectra of compound 3ea.


S-35

1H and

13C NMR spectra of compound 3fa.


S-36

1H and

13C NMR spectra of compound 3ga.


S-37

1H and

13C NMR spectra of compound 3ha.


S-38

1H and

13C NMR spectra of compound 3ia.


S-39

1H and

13C NMR spectra of compound 3ja.


S-40

1H and

13C NMR spectra of compound 3ka.


S-41

1H and

13C NMR spectra of compound 3la.


S-42

1H and

13C NMR spectra of compound 3ma.


S-43


S-44

1H and

13C NMR spectra of compound 3aa’.


S-45

ORTEP diagram of compound 3ah.


S-46

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 Å

Crystal system Monoclinic

Space group P 2(1)/c

Unit cell dimensions a = 9.2845(6) Å = 90°.

b = 8.1916(5) Å = 102.541(3)°.

c = 19.3256(12) Å = 90°.

Volume 1434.74(16) Å3

Z 4

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

S-47

ORTEP diagram of compound 3ai.


S-48

Table 1. Crystal data and structure refinement for 3ai.


Empirical formula C34 H32 B2 F8 N2




Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 7.2675(3) Å = 82.921(2)°.

b = 7.9484(4) Å = 83.610(2)°.

c = 27.5441(13) Å = 74.824(2)°.

Volume 1518.70(12) Å3

Z 2



F(000) 664



Index ranges -9

S-49

ORTEP diagram of compound 3aj.


S-50

Table 1. Crystal data and structure refinement for 3aj.


Empirical formula C36 H32 B2 F8 N2 O4




Crystal system triclinic

Space group P -1

Unit cell dimensions a = 10.5920(2) Å = 89.8660(10)°.

b = 11.1165(2) Å = 69.4220(10)°.

c = 14.8645(3) Å = 88.0730(10)°.

Volume 1637.55(5) Å3

Z 2



F(000) 752



Index ranges -14

S-51

11B NMR spectra of compound 3aa.

19

F NMR spectra of compound 3aa.


a convenient synthesis of quinolizinium salts through rh ... · s-1 a convenient synthesis of...

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