Table 1 Isolated yields of heterocycles from hydrogenation of nitroaldehydes 4a
Product yieldsb (%)
Entry
Reactant
RCHO
Catalyst
Monomer 5
Dimer 6
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
4a
4b
4c
4d
4d
4e
4f
4g
4h
4i
4i
4j
4k
4l
4l
4m
4n
4n
4o
4p
4q
4r
4s
2-O(CH2)2CH(CH3)CHO
2-CH2SCH2CH(CH3)CHO
2-O(CH2)3CHO
2-O(CH2)4CHO
2-O(CH2)4CHO
2-CH2O(CH2)3CHO
2-N(COPh)(CH2)4CHO
2-O(CH2)5CHO
2-O(CH2)2OCH2CH(CH3)CHO
2-O(CH2)2O(CH2)3CHO
2-O(CH2)2O(CH2)3CHO
2-O(CH2)2N(SO2Me)(CH2)3CHO
2-O[(CH2)2O]2CH2CH(CH3)CHO
2-O[(CH2)2O]2(CH2)3CHO
2-O[(CH2)2O]2(CH2)3CHO
2-O(CH2)9CH(CH3)CHO
2-O(CH2)11CHO
2-O(CH2)11CHO
3-O(CH2)2CH(CH3)CHO
3-O(CH2)4CHO
4-O(CH2)5CHO
4-O(CH2)2O(CH2)3CHO
4-O[(CH2)2O]2((CH2)3CHO
Pd
Pt
Pd
Pd
Pt
Pd
Pd
Pd
Pd
Pd
Pt
Pd
Pd
Pd
58
Pt
14(8)
20(8)
33(8)
—(9)
—
—(9)
22(9)
7(10)
—(10)
19(11)
22
36(11)
56(13)
75(14)
—
29(15)
27(16)
36
30(16)
—(16)
8(16)
64(18)
75
23(18)
–(18)
20(20)
37(20)
36(22)
18
—(22)
—(26)
6(18)
18(30)
19(32)
11
39(18)
17(20)
11(24)
22(26)
26(32)
Pd
Pd
Pd
Pd
Pd
Pt
6(9)
10(10)
—(12)c
7(13)
—(16)
Pt
a Reactions at ambient temperature with H2 (1 atm, 0.1MPa) using a substrate concentration of 4.763 1023 M in methanol with Pd (5.6 3 1025 g atom)
b
c
as 10% Pd on C and Pt (3 3 1024 g atom) as PtO2. Ring size in parentheses. Amino alcohol from reduction of CHO and NO2 groups also formed
(45%).
Table 2 Yields of monomer 5 and dimer 6 from hydrogenations of the
nitroaldehyde 4i with additivesa
b = 5.0502(1), c = 23.455(1) Å, b = 101.075(1)°, U = 1074.42(7) Å3, Z
= 2, Dc = 1.182 g cm23, crystal dimensions 0.35 3 0.15 3 0.11 mm, T =
173(1) K, Mo-Ka, radiation l = 0.71069 Å, m = 0.75 cm21. Data were
collected on a Nonius Kappa CCD diffractometer and of the total 6885
Yield (%)b
reflections measured, 2820 unique (Rint = 0.041). Refinement on F, Rw
=
Additive
5i
6i
0.052, R1 = 0.053 [for 1511 reflections with I > 3s(I)]. CCDC 182/1323.
.cif format.
—
19
30
33
45
21
36
—
—
—
33
Ag(OTf) 1 equiv.
Ag(OTf) 2 equiv.
La(OTf)3 1 equiv.
Glycine 1 equiv.c
1 P. N. Rylander, Catalytic Hydrogenation in Organic Synthesis,
Academic Press, London, 1979, p. 132.
2 H. Ina, M. Ito and C. Kibayashi, J. Org. Chem., 1996, 61, 1023.
3 E. M. Campi, W. R. Jackson and A. E. Trnacek, Aust. J. Chem., 1997,
50, 807; D. Anastasiou, E. M. Campi, H. Chaouk and W. R. Jackson,
Tetrahedron, 1992, 48, 7467.
4 A. L. J. Beckwith and W. B. Gara, J. Chem. Soc., Perkin Trans. 2, 1975,
593; L. Garanti and G. Zecchi, J. Heterocycl. Chem., 1993, 30, 559; G.
Broggini, L. Garanti, G. Molteni and G. Zecchi, Tetrahedron, 1997, 53,
3005.
5 G. D. Cuny and S. L. Buchwald, J. Am. Chem. Soc., 1993, 115, 2066; I.
Ojima, D. M. Iula and M. Tzamarioudaki, Tetrahedron Lett., 1998, 39,
4599.
a
Reactions using Pd/C in methanol under conditions in footnote a in
Table 1. b Isolated yield. c Glycine dissolved in a minimum amount of water
(0.2 ml) and added to reaction in methanol (85 ml).
We thank the Australian Research Council for support and
for provision of a postgraduate award (to TV) and Johnson
Matthey Pty Ltd for loan of precious metals.
6 C. Botteghi, R. Ganzerla, M. Lenarda and G. Moretti, J. Mol. Catal.,
1987, 40, 129; I. Amer and H. Alper, J. Am. Chem. Soc., 1990, 112,
3674.
7 Insight II (v 4.0.0) (Discover) Molecular Modelling System; Molecular
Simulations Inc., 9685 Scranton Road, San Diego, CA 92121-3752
(USA).
8 A. J. Leong, L. F. Lindoy, D. C. R. Hockless, G. F. Swiegers and S. B.
Wild, Inorg. Chim. Acta, 1996, 246, 371.
9 D. Parker and J. A. G. Williams, J. Chem. Soc., Perkin Trans. 2, 1995,
1305.
10 J. J. Christensen, D. J. Eatough and R. M. Izatt, Chem. Rev., 1974, 74,
351; R. M. Izatt, J. S. Bradshaw, K. Pawlak, R. L. Bruening and B. J.
Tarbet, Chem. Rev., 1992, 92, 1261.
11 A. P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M. Huxley,
C. P. McCoy, J. T. Rademacher and T. E. Rice, Chem. Rev., 1997, 97,
1515.
12 E. Ishow, A. Credi, V. Balzani, F. Spadola and L. Mandolini, Chem.
Eur. J., 1999, 5, 984.
Notes and references
† Crystal data for 5n: C25H33NO2, M = 379.54, monoclinic space group
P21/n, a = 9.3905(1), b = 23.1162 (5), c = 10.0908(2) Å, b = 99.648(1)°,
U = 2159.46(6) Å3, Z = 4, Dc = 1.167 g cm23, crystal dimensions 0.32
3 0.25 3 0.17 mm, T = 123(1) K, Mo-Ka, radiation l = 0.71069 Å, m =
0.73 cm21. Data were collected on a Nonius Kappa CCD diffractometer and
of the total 15 217 reflections measured, 4843 unique (Rint = 0.021).
Refinement on F, Rw = 0.039, R1 = 0.037 [for 3268 reflections with I >
3s(I)]. For 6a: C22H30N2O2, M = 354.49, orthorhombic space group Pbca,
a = 7.045(5), b = 16.646(1), c = 16.866(1) Å, U = 1977.80(2) Å3, Z = 4,
Dc = 1.190 g cm23, crystal dimensions 0.20 3 0.18 3 0.08 mm, T = 173
(1) K, Mo-Ka, radiation l = 0.71069 Å, m = 0.76 cm21. Data were
collected on a Nonius Kappa CCD diffractometer and of the total 13313
reflections measured, 2819 unique (Rint = 0.106). Refinement on F, Rw
0.052, R1 0.064 [for 825 reflections with I 3s(I)]. For 6g:
C24H34N2O2, M = 382.54, monoclinic space group P21/c, a = 9.2424(5),
=
=
>
Communication 9/04168K
1464
Chem. Commun., 1999, 1463–1464