Supporting Information for Angew. Chem. Int. Ed. Z53942 © Wiley-VCH 2004 69451 Weinheim, Germany
Supporting Information
for
Angew. Chem. Int. Ed. Z53942
© Wiley-VCH 2004
69451 Weinheim, Germany
1
Efficient Asymmetric Hydrogenation of Pyridines
Frank Glorius,* Nick Spielkamp, Sigrid Holle, Richard Goddard, Christian W. Lehmann Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Contents
(1) General information.
(2) Values of optical rotation.
(3) Data of chiral GC and GC/MS analysis. (For compounds 3f, 6g and 6j 1H and 13C NMR
spectra are provided instead).
General information
All new compounds were fully characterized. The optical purity of piperidines 3 was determined by
GC-analysis of the corresponding trifluoroacetamide derivatives using an Ivadex 1 (PS086) column
(25m x 0.25mm x 0.25µm) or a comparable BGB-177 column (30m x 0.25mm x 0.25µm). Alkylated
piperidine 7 was measured underivatized using the same chiral colums. In all cases, the identity of
the enantiomers was verified by comparison to independently prepared racemates. The optical
purity of aminales 6g and 6j was determined by NMR.
Sources of the catalysts used in this study: 5% Ru/C from Roth (2-3608),
PtO2 from Heraeus,
10% Pt/C from Degussa,
5% Rh/C from Heraeus,
wet (50% H2O) 0.5% Rh/4.5% Pd/C from Heraeus (K-0237),
10% Pd/C from Fluka (75990),
moist 20% (dry basis) Pd(OH)2/C from Aldrich (21,291-1).
2
[α]D20
Values of optical rotation
Piperidinium
hydrochlorides Optical rotation Literature
3a = -3.7 (c 0.5, EtOH) = -3.9 (c 0.46, EtOH)1
3b 3b
= +6.6 (c 1.8, EtOH)
= +6.4 (c 0.4, EtOH)
= +6.2 (c = 0.43, EtOH)2
3c = -25.0 (c 1.1, CHCl3) -
N-Boc of 3c = +34.3 (c 1.7, CHCl3) = +35.9 (c = 2.0, CHCl3)3
3d = -3.2 (c 1.2, MeOH) = -3 (c = 0.6, MeOH)4
3e = -1.2 (c 1.0, CHCl3) -
3f = +4.2 (c 1.9, MeOH) -
6g = +49.3 (c 1.1, MeOH) -
3i = -5.3 (c 1.1, CHCl3) -
3j = -13.3 (c 1.1, MeOH) -
6j = +43.0 (c 0.9, MeOH) -
7 = +1.9 (c 1.0, CHCl3) -
1 M. J. Munchhof, A. I. Meyers, J. Org. Chem. 1995, 60, 7084. 2 N. Yamazaki, C. Kibayashi, Tetrahedron Lett. 1997, 38, 4623. 3 D. J. Hart, J. Li, W.-L. Wu, A. P. Kozikowski, J. Am. Chem. Soc. 1995, 117, 9369. 4 L. Micouin, T. Varea, C. Riche, A. Chiaroni, J.-C. Quirion, H.-P. Husson, Tetrahedron Lett. 1994, 35, 2529.
[α]D20
[α]D20
[α]D20
[α]D20
[α]D20
[α]D20
[α]D20
[α]D20
[α]D20
[α]D20
[α]D26 [α]
D26
[α]D23[α]
D23
[α]D20 [α]
D20
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28