Supporting Information

Xueling Mi, † Sanzhong Luo, ‡ Jin-Pei Cheng*,†, ‡

Department of Chemistry, State Key Laboratory of Elemento-organic Chemistry, Nankai

University, Tianjin, 300071, China and Center for Molecular Science, Institute of

Chemistry, Chinese Academy of Sciences, Beijing, 100080, China.

jpcheng@nankai.edu.cn, chengjp@mail.most.gov.cn

S1
 Table of Contents

General Procedure for Synthesis of 1a, 1b, 1c S3-S4

Spectra for 1a, 1b, 1c S5-S7

General Procedure for the Synthesis of 3-Benzylaminoquinuclidine S8

NMR Spectra for 3-Benzylaminoquinuclidine S9

Experiment to Determine the Stability of Compound 1b in Methanol S10-S11

Experiment to Determine the Stability of Compound 1b in Methanol in the Presence of

Aldehyde S12-S13

General Procedure for the Baylis-Hillman Reactions between Aldehydes and Activated

Alkenes in the Presence of 1b S14

1
H NMR Spectra for 2a-2p S15-S22
1
H NMR Spectra for 3a-3f S23-S25
1
H NMR Spectra for 4a-4e S26-S28

Reference S29

S2
 H
General Procedure for the Synthesis of 1a:
N N N Br- The synthesis of amino ionic liquid followed
1a:
C4H9n the published procedure (J. Am. Chem. Soc.
N
2002, 124, 926-927): To a stirred solution of N-
butylimidazole (3.10g, 25mmol) in ethanol was added 3-bromopropylamine hydro-
bromide (5.47g, 25mmol). The solution was heated to reflux for 24 hrs. The ethanol was
then removed in vacuo and the solid residue was dissolved in a minimal quantity of water
and brought to about pH=8 by the addition, in small portions, of solid KOH. The water
solution was then concentrated to dryness and the residue was extracted with ethanol-
THF. The combined extracts were concentrated to give the product amino imidazolium
bromide (6.04g, 96%) as a pale yellow viscous liquid.
To a solution of the synthetic amino imidazolium bromide (3.93g, 15mmol) in dry
methanol was added 3-quinuclidine (2.81g, 22.5mmol). After stirring for 12 h at room
temperature, the reaction was cooled to 0°C and sodium borohydride (1.28g, 33.8mmol)
was added in small portions. The solution was stirred for 4 h, followed by adding small
quantity of water. The resulting mixture was then stirred for additional 30 min and
concentrated to dryness. The residue was extracted with chloroform and the extract was
concentrated, followed by extensive washing with diethyl ether to provide the expected
product 1a (4.76g, 86%) as a yellow viscous liquid.
1
H NMR (CDCl3, 300 MHz): δ 9.87 (s, 1H), 7.50 (s, 1H), 7.41 (s, 1H), 4.41 (t, J= 7.2 Hz,
2H), 4.27 (t, J= 7.2 Hz, 2H), 3.05 (m, 1H), 2.71-2.60 (m, 6H), 2.53 (m, 2H), 2.07 (m, 2H),
1.85 (m, 2H), 1.75 (m, 1H), 1.65-1.58 (m, 2H), 1.32 (m, 4H), 0.91 (t, J= 7.2 Hz, 3H).

General Procedure for the Synthesis of 1b:

H The sodium tetrafluoroborate (1.81g,
BF4-
1b: N N N 16.5mmol) was added to a solution of the
C4H9n
N synthetic amino imidazolium bromide (3.93g,
15mmol) in ethanol/water and stirred for 3
days. The suspension was filtered to remove the precipitated bromide salt and the organic
phase was concentrated. The residue was then re-dissolved in small amount of
chloroform, and filtered to remove the inorganic salt. The solvent was removed in vacuo
to afford yellow viscous liquid (4.19g, 91%)
The synthesis of 1b followed the similar procedure with 1a. With 4.04g of
imidazolium tetrafluoroborate (15mmol), 5.13g of 1b was obtained (91%) as a yellow
viscous liquid.

IR (cm-1): 2927.93, 2854.64, 1161.82, 1046.81, 742.363; 1H NMR (CDCl3, 300 MHz): δ
10.45 (s, 1H), 7.49 (s, 1H), 7.38 (s, 1H), 4.45 (t, J= 7.2 Hz, 2H), 4.29 (t, J= 7.2 Hz, 2H),
3.03 (m, 1H), 2.71-2.64 (m, 6H), 2.58 (m, 2H), 2.07 (m, 2H), 1.85 (m, 2H), 1.74 (m, 1H),
1. 63 (m, 2H), 1.35-1.28 (m, 4H), 0.90 (t, J= 7.2 Hz, 3H); 13C NMR (CDCl3, 75 MHz): δ
137.4, 122.5, 121.7, 58.1, 56.5, 55.0, 49.8, 47.5, 46.9, 43.5, 32.2, 30.7, 25.9, 24.9, 19.5,
19,0, 13.5; HRMS for C17H31N4+ (M+), calcd. 291.2549; found, 291.2540.

S3
 General Procedure for the Synthesis of 1c:
H
PF6- The potassium hexafluorophosphate
1c: n
N N N (3,04g, 16.5mmol) was added to a solution
C4H9
N of the synthetic amino imidazolium bromide
(3.93g, 15mmol) in ethanol/water and stirred
for 3 days. The suspension was filtered to remove the precipitated bromide salt and the
organic phase was concentrated. The residue was then dissolved in small amount of
chloroform, filtered to remove the remained inorganic salt, then concentrated to provide
yellow viscous liquid (3.84g, 78%).
The synthesis of 1c followed the similar procedure. With 5.49g of imidazolium
hexafluorophosphate (15mmol), 5.60g of 1c (83%) was obtained as a pale yellow viscous
liquid.
1
H NMR (CDCl3, 300 MHz): δ 9.53 (s, 1H), 7.46 (s, 1H), 7.38 (s, 1H), 4.37 (t, J= 7.2 Hz,
2H), 4.22 (t, J= 7.2 Hz, 2H), 3.04 (m, 1H), 2.71-2.66 (m, 6H), 2.56 (m, 2H), 2.04 (m, 2H),
1.83 (m, 2H), 1.76 (m, 1H), 1. 61 (m, 2H), 1.36-1.28 (m, 4H), 0.91 (t, J= 7.2 Hz, 3H).

S4
1
H NMR Spectra of Compound 1a

H
N N N Br-
1a:
C4H9n
N

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
ppm (f1)

1
H NMR Spectrum of Compound 1b

H
1b: N N N BF4-
C4H9n
N

11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (t1)

S5
13
C NMR Spectrum of Compound 1b

H
1b: N N N BF4-
C4H9n
N

140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

DEPT 135 Spectrum of Compound 1b

S6
HRMS of Compound 1b

1
H NMR Spectrum of Compound 1c

H
PF6-
1c: N N N
C4H9n
N

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
ppm (f1)

S7
 General Procedure for the Synthesis of 3-Benzylamino-
NHCH2Ph quinuclidine
N Benzyl amine (0.713 g, 6.67 mmol) was added to a solution of
3-quinuclidinone (1.254 g, 10 mmol) in dry methanol (15 mL).
The solution was stirred at room temperature for 12 h and then cooled to 0°C. To the
solution was added portion wise sodium borohydride (0.418 g, 11 mmol). The resulting
mixture was then stirred at room temperature for another 4 h, followed by adding small
quantity of water. The resulted mixture was stirred for 30 min and then concentrated to
dryness. The residue was extracted with chloroform. After concentration, the residue was
dissolved in a mixture of acetone and n-propyl alcohol (2/1). The expected amine was
precipitated under the form of the dihydrochloride by the addition of a 2 N ethanolic
hydrogen chloride solution until the pH was equal to 1. The white solid was filtered,
washed with acetone, then recrystallised twice in an ethanol-methanol mixture (1/1) to
provide the desired product as pale yellow solid (1.392 g, 72%).
To a solution of the synthetic dihydrochloride (1.156 g, 4 mmol) in water (40 mL) was
added portion wise potassium hydroxide (0.840 g, 12 mmol) at 0°C. The solution was
stirred for 1 h at room temperature and then concentrated to dryness. The residue was
extracted with chloroform. After concentration the expected 3-benzylaminoquinuclidine
was obtained as a pale yellow viscous liquid (0.816 g, 94%).
1
H NMR (CDCl3, 300 MHz) δ 7.34 (m, 5H), 3.76 (m, 2H), 3.12 (m, 1H), 2.81-2.76 (m,
6H), 1.87 (m, 1H), 1.68 (m, 2H), 1.46 (m, 2H); 13C NMR (CDCl3, 75 MHz) δ 128.4,
128.1, 126.9, 56.8, 54.3, 51.5, 47.7, 47.1, 26.4, 25.0, 20.2; MS for C14H21N2 (M+1), calcd.
217.16; found, 217.21.

S8
1
H NMR Spectrum of 3-Benzylaminoquinuclidine

NHCH2Ph
N

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

13
C NMR Spectrum of 3-Benzylaminoquinuclidine

NHCH2Ph
N

140 130 120 110 100 90 80 70 60 50 40 30 20 10

ppm (t1)

S9
 Experiment to Determine the Stability of Compound 1b in Methanol
1
H NMR Spectra of Compound 1b in CD3OD at the time indicated.
Full Spectra:

t=0

t=2h

t=4h

t=10h

t=24h

t=48h

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S10
Chemical Shift from 6.0 to 10.0:

t=0

t=2h

t=4h

t=10h

t=24h

t=48h

9.50 9.00 8.50 8.00 7.50 7.00 6.50

ppm (f1)

S11
Experiment to Determine the Stability of Compound 1b in Methanol in the Presence
of Aldehyde

After mixing p-chlorobenzaldehyde (71mg, 0.5mmol), 1b (57mg, 0.15mmol) and

CD3OD (41µL, 1mmol, 2.0 equiv.) together, 15µL of the resulting solution was taken out
to do 1H NMR experiment in CDCl3 at the time indicated.
Full Spectra:

t=0

t=2h

t=4h

t=10h

t=24h

t=48h

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (f1)

S12
Chemical Shift from 6.0 to 11.0:
t=0

t=2h

t=4h

t=10h

t=24h

t=48h

10.0 9.0 8.0 7.0

ppm (f1)

S13
General Procedure for the Baylis-Hillman Reactions Between Aldehydes and
Activated Alkenes in the Presence of 1b

To the solution of 1b (57mg, 0.15mmol) in CH3OH (41µL, 2.0 equiv.) was added
aldehyde (0.5mmol) and activated alkene (0.75mmol). The reaction homogeneous
solution was stirred at ambient temperature and monitored by TLC. After indicated
reaction time the reaction solution was concentrated and the residue was extracted with
diethyl ether. The combined extracts were concentrated and the crude product was
purified by flash chromatography on silica gel to afford the desired product. Catalyst
recycling study was conducted similarly. After extraction with diethyl ether to separate
the products, the solvent was removed in vacuum and the resulting catalyst was reused
directly for the next run.

S14
1
H NMR Spectra of 2a-2p

OH O

OCH3
2a:
Cl

7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH O
2b:
OCH3

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S15
 OH O
2c: OCH3

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (t1)

OH O
2d:
OCH3

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (t1)

S16
 OH O

OCH3
2e:

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH O

2f: OC2H5

Cl

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S17
 OH O

OC4H9
2g:
Cl

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH O

2h: OCH3

H3 C

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S18
 OH O

2i: OCH3

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH O

OCH3
2j:
O2 N

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S19
 OH O

OCH3
2k:
NO2

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH O

OCH3
2l:

NO2

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (f1)

S20
 OH O

OCH3
2m:
N

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (f1)

OH O

OCH3
2n:
N

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (f1)

S21
 OH O

OCH3
2o:
N

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 -1.0
ppm (f1)

OH O
O
2p: OCH3

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (f1)

S22
1
H NMR Spectra of 3a-3f

OH
CN
3a:

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH
CN
3b:
Cl

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S23
 OH
CN
3c:
H3C

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH
CN
3d:
H3CO

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S24
 OH
CN
3e:
O2N

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (f1)

OH
CN
3f:
N

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (f1)

S25
1
H NMR Spectra of 4a-4e

OH O
4a:

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH O
4b:

Cl

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S26
 OH O
4c:

H3 C

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

OH O
4d:

O2 N

15.0 10.0 5.0 0.0

ppm (f1)

S27
 OH O

4e: O

7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (f1)

S28
Reference:
(1) Bates, E. D.; Mayton, R. D.; Ntai, I.; Davis, J. H. J. Am. Chem. Soc. 2002, 124, 926-
927
(2) Langlois, M.; Meyer, C.; Soulier, J. L. Syn. Commun. 1992, 22, 1895-1911.
(3) Aggarwal, V. K.; Emme, I.; Fulford, S. Y. J. Org. Chem., 2003, 68, 692-700.
(4) João, N. R.; Carlos, A. M. A.; António, G. S. Tetrahedron 2001, 57, 4189-4193.
(5) Luo, S. Z.; Zhang, B. L.; He, J. Q.; Janczuk, A.; Wang, P. G.; Cheng, J. -P.
Tetrahedron Lett. 2002, 43, 7369.
(6) Luo, S. Z.; Wang, P. G.; Cheng, J. -P. J. Org. Chem. 2004, 69, 555.
(7) Luo, S. Z; Mi, X. L.; Wang, P. G.; Cheng, J.-P. Tetrahedron Lett. 2004, 45, 5171.

S29