A. Leganza, C. Bezze, C. Zonta, F. Fabris, O. De Lucchi, A. Linden
FULL PAPER
C12H10BrN3 (275.01): calcd. C 52.20, H 3.65, N 15.22; found C
52.16, H 3.63, N 15.28.
asymmetric unit contains one monovalent Pd complex cation, one
chloride anion and 1.5 disordered toluene molecules distributed
over two sites. One of the symmetry-independent toluene molecules
is in a general position, while another is in a center of inversion.
Both toluene molecules are disordered and the disordered
model was established with the aid of suitable geometric and
atomic displacement parameter constraints and restraints.
CCDC-277072 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Synthesis of 3: A solution of ketimine 1 (5.0 g, 18.1 mmol) and
ketone 2 (0.3 g, 1.0 mmol, 0.06 equiv.) in xylenes (50 mL) was re-
fluxed for 4 h. The mixture was cooled to 40 °C and filtered. The
filtrate was washed with toluene (4×5 mL) and the compound was
dried in an oven at 50 °C to give 3 as colorless needles (3.5 g,
6.1 mmol, 72%), m.p. 235–237 °C. IR (KBr): ν = 3384, 3047 (Ph),
˜
1591 (Py and Ph), 1498 (Py and Ph) cm–1. 1H NMR (300 MHz,
[D6]DMSO, 25 °C): δ = 8.66 (d, J = 4.8 Hz, 2 H), 7.94–7.84 (m, 4
H), 7.64 (s, 2 H), 7.43 (m, 2 H), 7.05 (dd, J = 8.4 and 2.4 Hz, 2
H), 6.84 (d, J = 8.4 Hz, 2 H), 6.68 (d, J = 2.4 Hz, 2 H) 3.89 (s, 1
H) ppm. 13C NMR (75 MHz, [D6]DMSO, 25 °C): δ = 160.2, 148.3,
142.7, 137.4, 130.1, 130.0, 129.0, 123.4, 120.9, 118.3, 107.6,
69.0 ppm. ESI-MS: m/z = 534 [M+H]+. C24H17Br2N5 (534.98):
calcd. C 53.86, H 3.20, N 13.08; found C 53.96, H 3.22, N 12.99.
Acknowledgments
This work was co-funded by MIUR within the PRIN framework.
Synthesis of 6: A solution of ketimine 4 (3.2 g, 13.3 mmol) and
ketone 5 (0.3 g, 1.3 mmol, 0.1 equiv.) in acetonitrile (250 mL) was
refluxed to complete dissolution. The mixture was cooled to 0 °C
and filtered. The filtrate was washed with cold acetonitrile
(4×5 mL) and the compound was dried in an oven at 50 °C to give
6 as a yellow powder (0.78 g, 1.6 mmol, 12%), m.p. 201–202 °C. IR
[1] a) J. Tröger, J. Prakt. Chem. 1887, 36, 225–245; b) M. Demeu-
nynck, A. Tatibouet, “Recent Developments in Tröger’s Base
Chemistry”, in Progress in Heterocyclic Chemistry (Eds.: G. W.
Gribble, T. L. Gilchrist), Pergamon, Oxford, UK, 1999; c) B. G.
Bag, Curr. Sci. 1995, 68, 279–288; d) T. Mas, C. Pardo, F. Sa-
lort, J. Elguero, M. R. Torres, Eur. J. Org. Chem. 2004, 5, 1097–
1104; e) A. Hansson, J. Jensen, O. F. Wendt, K. Wärnmark,
Eur. J. Org. Chem. 2003, 4, 3179–3188; f) C. Solano, D. Svens-
son, Z. Olomi, J. Jensen, O. F. Wendt, K. Wärnmark, Eur. J.
Org. Chem. 2005, 6, 3510–3517.
(KBr): ν = 3312, 1611, 1590, 1468, 1322, 1253, 1093, 1024,
˜
1
701 cm–1. H NMR (300 MHz, [D6]DMSO, 25 °C): δ = 8.91 (s, 2
H), 7.92 (d, J = 9.0 Hz, 2 H), 7.71 (d, J = 6.6 Hz, 4 H), 7.44 (m, 8
H), 6.88 (d, J = 9.0 Hz, 2 H) 4.29 (s, 1 H) ppm 13C NMR (75 MHz,
[D6]DMSO, 25 °C): δ = 151.0, 140.9, 136.1, 128.4, 128.0, 127.8,
127.3, 124.5, 123.5, 115.0, 69.9 ppm. ESI-MS: m/z = 466 [M+H]+.
C26H19N5O4 (465.14): calcd. C 67.09, H 4.11, N 15.05; found C
66.89, H 4.09, N 14.99.
ˇ
[2] a) S. Stoncˇius, E. Butkus, A. Zilinskas, K. Larsson, L.
Öhrström, U. Berg, K. Wärnmark, J. Org. Chem. 2004, 69,
5196–5203; b) B. Dolenský, M. Valík, D. Sýkora, V. Král, Org.
Lett. 2005, 7, 67–70; c) S. Paliwal, S. Geib, C. S. Wilcox, J. Am.
Chem. Soc. 1994, 116, 4497–4498; d) B. G. Bag, G. von Kied-
rowski, Angew. Chem. Int. Ed. 1999, 38, 3713–3714.
[3] A. Albert, H. Yamamoto, J. Chem. Soc. C 1968, 1944–1949.
[4] H. Hagen, R.-D. Kohler, 1987, US 4667035.
[5] a) P. Molina, A. Arques, I. Cartagena, R. Obón, Tetrahedron
Lett. 1991, 32, 2521–2524; b) P. Molina, A. Arques, A.
Tárraga, M. d. R. Obón, C. Foces-Foces, N. Jagerovic, J. El-
guero, Tetrahedron 1998, 54, 997–1004.
[6] a) K. E. Frank, J. Aubè, Tetrahedron Lett. 1998, 39, 7239–7242;
b) K. E. Frank, J. Aubè, J. Org. Chem. 2000, 65, 655–666.
[7] a) L. Y. Ukhin, Z. I. Orlova, V. N. Khrustalev, Russ. Chem.
Bull. 2004, 46, 1931–1935; b) L. Y. Ukhin, L. G. Kuz’mina,
Russ. Chem. Bull. 2004, 53, 2262–2268.
[8] Synthesis of 4: R. I. Fryer, L. H. Sternbach, 1969, US 3440281.
[9] F. Trécourt, G. Breton, V. Bonnet, F. Mongin, F. Marsais, G.
Quéguiner, Tetrahedron 2000, 56, 1349–1360.
Synthesis of Palladium(II) Complex 11: A solution of 3 (0.5 g,
9.3 mmol) and PdCl2 (0.1 g, 0.6 mmol) in toluene (3 mL) was re-
fluxed for 5 min. The mixture was filtered and cooled. The filtered
solution was left to concentrate slowly, yielding 11 as red, crystal-
line prisms (35 mg, 0.02 mmol).
Crystal Data for 11·1.5toluene: C34.5H29Br2Cl2N5Pd, Mr = 850.76,
monoclinic, space group C2/c, a = 24.6800(4), b = 17.4701(3), c =
17.4364(3) Å, β = 116.632(1)°, V = 6736.1(2) Å–3, Z = 8, DX
=
=
1.678 gcm–3, crystal dimensions: 0.15×0.18×0.23 mm,
T
–113 °C, Nonius KappaCCD area-detector diffractometer, Mo-Kα
radiation, λ = 0.71073 Å, µ = 3.122 mm–1, absorption correction
based on analysis of equivalent reflections (SORTAV), transmission
factors (min./max.) 0.531/0.611, 2θmax = 52°, 52974 measured re-
flections, 6633 symmetry-independent reflections, 5301 reflections
with I Ͼ 2σ(I), refinement on F2 with SHELXL-97, 451 param-
eters, 111 restraints, R(F) [I Ͼ 2σ(I) reflections] = 0.035, wR(F2)
(all reflections) = 0.091, S(F2) = 1.063, ∆ρmax = 0.58 eÅ–3. The
[10] a) J. Jensen, J. Tejler, K. Wärnmark, J. Org. Chem. 2002, 67,
6008–6014; b) A. Hansson, T. Wixe, K.-E. Bergquist, K.
Wärnmark, Org. Lett. 2005, 7, 2019–2022.
Received: February 27, 2006
Published Online: April 26, 2006
2990
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 2987–2990