PINCER LIGANDS BASED ON α-AMINO ACIDS: I.
859
dialdehyde II, 2 g of magnesium sulfate, 2 g of 3-Å
molecular sieves, and 100 ml of anhydrous ethanol.
Found, %: C 56.16; H 6.55; N 22.65. C20
culated, %: C 55.93; H 6.34; N 22.83.
H
27
N
7
O
4
. Cal-
Yield 3.08 g (68%), brown powder, mp 58–60°C. IR
(
S,S)-2,5-Bis[1-ethoxycarbonyl-2-(1H-imidazol-
–
1
spectrum (KBr), ν, cm : 1628 (C=N), 1733 (C=O).
4
-yl)ethylaminomethyl]pyrrole (IX) was synthesized
as described above for amine VIII from 2.27 g
(5 mmol) of Schiff base VI and 0.57 g (15 mmol)
1
H NMR spectrum (CD OD), δ, ppm: 1.23 t (6H,
3
CH , J = 7.1 Hz), 3.00–3.20 m (4H, CH ), 4.15–4.35 m
3
2
(
2H, CH), 4.17 q (4H, OCH , J = 7.0 Hz), 6.52 s (2H,
2
NaBH in 75 ml of ethanol. Yield 1.49 g (65%), light
4
CH), 6.79 s (2H, CH), 7.58 s (2H, CH), 7.87 s (2H,
HC=N). Found, %: C 58.35; H 6.12; N 21.43.
brown powder, mp 30–40°C. IR spectrum (KBr), ν,
–
1
1
cm : 1730 (C=O). H NMR spectrum (CD OD), δ,
3
C H N O . Calculated, %: C 58.27; H 6.00; N 21.62.
22
27
7
4
ppm: 2.08 t (6H, CH , J = 7.1 Hz), 2.94 d (4H, CH ,
3
2
J = 6.6 Hz), 3.45–3.90 m (6H, CH NHCH), 4.13 q
2
(
S,S)-2,5-Bis(1-methoxycarbonyl-3-methylsul-
fanylpropylaminomethyl)pyrrole (VII). A solution of
.07 g (5 mmol) of Schiff base IV in 75 ml of metha-
(
4H, OCH , J = 7.1 Hz), 5.80 s (2H, CH), 6.67 s (2H,
2
CH), 7.41 s (2H, CH). Found, %: C 57.94; H 6.11;
N 21.22. C H N O . Calculated, %: C 57.75; H 6.83;
2
22
31
7
4
nol was cooled to –30°C, 0.57 g (15 mmol) of sodium
tetrahydridoborate was added, and the mixture was
stirred for 1 h at –30°C and for 1 h at room tempera-
ture. A solution of 0.9 g (15 mmol) of acetic acid in
N 21.43.
ACKNOWLEDGMENTS
1
0 ml of methanol was then added, and the mixture
This study was performed under financial support
by the Belarussian Foundation for Basic Research
was stirred for 1 h and evaporated under reduced pres-
sure. The residue was extracted with diethyl ether, the
extract was filtered and concentrated under reduced
pressure, 100 ml of hexane was added, and the oily
material was separated, washed with hexane, and dried
at 45°C under reduced pressure. Yield 1.52 g (73%),
light brown oily substance. IR spectrum (KBr), ν,
(
project no. Kh06R-025) and by the Russian Founda-
tion for Basic Research (project nos. 06-03-81026, 05-
03-32684).
The authors are thankful to Prof. Yu.A. Ustynyuk
for setting the problem and helpful discussions.
–
1
1
cm : 1733 (C=O). H NMR spectrum (CDCl ), δ,
ppm: 1.60–1.95 m (4H, CH ), 1.99 s (6H, SCH ), 2.5 s
3
REFERENCES
2
3
(
3
5
4H, CH , J = 7.2 Hz), 3.34 t (2H, CH, J = 6.8 Hz),
1. Guerriero, P., Tamburini, S., and Vigato, P.A., Coord.
Chem. Rev., 1995, vol. 139, p. 17; Vigato, P.A. and
Tamburini, S., Coord. Chem. Rev., 2004, vol. 248,
p. 1717; Gerbeleu, N.V., Arion, V.B., and Burgess, J.,
Template Synthesis of Macrocyclic Compounds, Wein-
heim: Wiley, 1999, chaps. 2, 3.
2
.59 d (4H, CH N, J = 7.4 Hz), 3.65 s (6H, OCH ),
2
3
.77 s (2H, CH). Found, %: C 52.02; H 7.63; N 10.27.
C H N O S . Calculated, %: C 51.77; H 7.48; N 10.11.
18
31
3
4 2
(
S,S)-2,5-Bis[2-(1H-imidazol-4-yl)-1-methoxy-
carbonylethylaminomethyl]pyrrole (VIII). A solu-
tion of 2.13 g (5 mmol) of Schiff base V in 75 ml of
methanol was cooled to –30°C, 0.57 g (15 mmol) of
sodium tetrahydridoborate was added, and the mixture
was stirred for 1 h at –30°C and for 1 h at room tem-
perature. A solution of 0.9 g (15 mmol) of acetic acid
in 10 ml of methanol was then added, and the mixture
was stirred for 1 h and evaporated under reduced
pressure. The residue was extracted with acetone, the
extract was filtered and concentrated under reduced
pressure, 100 ml of diethyl ether was added, and the
precipitate was filtered off, washed with diethyl ether,
and dried at 45°C under reduced pressure. Yield 1.50 g
2
. Solomon, E.I., Sundaram, U.M., and Machonkin, T.E.,
Chem. Rev., 1996, vol. 96, p. 2563; Que, L. and
Ho, R.Y.N., Chem. Rev., 1996, vol. 96, p. 2607; Wal-
lar, B.J. and Lipscomb, J.D., Chem. Rev., 1996, vol. 96,
p. 2659.
3. Vahrenkamp, H., Acc. Chem. Res., 1999, vol. 32, p. 589;
Pierre, J.-L., Chem. Soc. Rev., 2000, p. 251.
4
5
6
. Thomas, Ch.M. and Ward, T.R., Chem. Soc. Rev., 2005,
p. 337.
. Jasat, A. and Dolphin, D., Chem. Rev., 1997, vol. 97,
p. 2267; Fenton, D.E., Chem. Soc. Rev., 1999, p. 159.
. Borisova, N.E., Ustynyuk, Yu.A., Reshetova, M.D., Alek-
sandrov, G.G., Eremenko, I.L., and Moiseev, I.I., Mende-
leev Commun., 2003, p. 202; Kataev, E.A., Resheto-
va, M.D., and Ustynyuk, Yu.A., Izv. Ross. Akad. Nauk,
Ser. Khim., 2004, p. 322; Borisova, N.E., Usty-
nyuk, Yu.A., Reshetova, M.D., Aleksandrov, G.G., Ere-
menko, I.L., and Moiseev, I.I., Izv. Ross. Akad. Nauk, Ser.
Khim., 2004, p. 326.
(
70%), light brown powder, mp 41–43°C. IR spectrum
–
1
1
(KBr), ν, cm : 1735 (C=O). H NMR spectrum
(
CD OD), δ, ppm: 2.96 d (4H, CH , J = 6.5 Hz),
3
2
3
5
.64 s (6H, OCH ), 3.45–3.90 m (6H, CH NHCH),
3 2
.85 s (2H, CH), 6.85 s (2H, CH), 7.69 s (2H, CH).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 6 2007