supporting information - wiley-vch.de file(25m x 0.25mm x 0.25µm) or a comparable bgb-177 column...

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

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