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Diastereoselective Hydrogenation of Substituted Quinolines to Enantiomerically Pure Decahydroquinolines
Article first published online: 9 FEB 2010
DOI: 10.1002/adsc.200900763
Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Heitbaum, M., Fröhlich, R. and Glorius, F. (2010), Diastereoselective Hydrogenation of Substituted Quinolines to Enantiomerically Pure Decahydroquinolines. Adv. Synth. Catal., 352: 357–362. doi: 10.1002/adsc.200900763
Publication History
- Issue published online: 17 FEB 2010
- Article first published online: 9 FEB 2010
- Manuscript Revised: 31 DEC 2009
- Manuscript Received: 30 NOV 2009
Funded by
- Deutsche Forschungsgemeinschaft
- Fonds der Chemischen Industrie
- Alfried Krupp Prize for Young University Teachers of the Alfried Krupp von Bohlen und Halbach Foundation
- 1See for example:
- 1a
- 1b
- 2Reviews on the asymmetric/diastereoselective hydrogenation of heteroaromatics:
- 2a
- 2b
- 2c
- 2d
- 2e, , Top. Catal. 2003, 25, 43. For some recent reviews on asymmetric hydrogenation, see:
- 2f, Angew. Chem. 2008, 120, 2592;Angew. Chem. Int. Ed. 2008, 47, 2556;Direct Link:Direct Link:
- 2g
- 2h
- 2i
- 2j
- 2k
- 2l
- 2m, , , , , , , Angew. Chem. 2007, 119, 6075;Angew. Chem. Int. Ed. 2007, 46, 5971;Direct Link:Direct Link:
- 2n
- 2o, , , Angew. Chem. 2006, 118, 4850;Angew. Chem. Int. Ed. 2006, 45, 4732.Direct Link:Direct Link:
- 3For some asymmetric hydrogenations of pyridines, see:
- 3a
- 3b, , Angew. Chem. 2007, 119, 4646;Angew. Chem. Int. Ed. 2007, 46, 4562;Direct Link:Direct Link:
- 3c
- 3d
- 3e, , , , Proc. Natl. Acad. Sci. USA 2004, 101, 11960;
- 3f, , , , , Angew. Chem. 2004, 116, 2910;Angew. Chem. Int. Ed. 2004, 43, 2850.Direct Link:Direct Link:
- 4For the asymmetric hydrogenation of quinolines, see:
- 4a
- 4b
- 4c, , , , , , , , , , Angew. Chem. 2008, 120, 8592;Angew. Chem. Int. Ed. 2008, 47, 8464;Direct Link:Direct Link:
- 4d
- 4e
- 4f, , , J. Organomet. Chem. 2007, 692, 365;
- 4g
- 4h
- 4i, , , , Angew. Chem. 2006, 118, 2318;Angew. Chem. Int. Ed. 2006, 45, 2260;Direct Link:Direct Link:
- 4j
- 4k
- 4l
- 4m
- 4n, , , , , J. Am. Chem. Soc. 2003, 125, 10536. For impressive organocatalyzed transfer hydrogenations, see:
- 4o
- 4p, , , Angew. Chem. 2006, 118, 3765;Angew. Chem. Int. Ed. 2006, 45, 3683.Direct Link:Direct Link:
- 5Anilines are readily available starting materials. For C
![[BOND]](http://onlinelibrarystatic.wiley.com/undisplayable_characters/00f8ff.gif)
H activations using anilines as precursors for the synthesis of heterocyclic products, see: - 5a, , , , Angew. Chem. 2009, 121, 7024;Angew. Chem. Int. Ed. 2009, 48, 6892;Direct Link:Direct Link:
- 5b, , , , , Angew. Chem. 2008, 120, 7340;Angew. Chem. Int. Ed. 2008, 47, 7230, and references cited therein.Direct Link:Direct Link:
- 6See Supporting Information for further details.
- 7For some regioselective hydrogenations of the carbocyclic ring of quinolines, see:
- 7a
- 7b
- 8For a general review on the application of chiral auxiliary, see: , , Synthesis 2006, 2996.
- 9
- 9aX-ray crystal structure analysis of 3a: formula C17H24N2O2, M=288.38, colorless crystal 0.25×0.20×0.20 mm, a=7.2876(4), b=11.5870(6), c=18.9300(10) Å, V=1598.48(15) Å3, ρcalc=1.198 g cm−3, μ=0.625 mm−1, empirical absorption correction (0.859≤T≤0.885), Z=4, orthorhombic, space group P212121 (No. 19), λ=1.54178 Å, T=223(2) K, ω and ϕ scans, 8218 reflections collected (±h, ±k, ±l), [(sinθ)/λ]=0.60 Å−1, 2678 independent (Rint=0.050) and 2231 observed reflections [I≥2σ(I)], 194 refined parameters, R=0.065, wR2=0.184, Flack parameter −0.1(7), max. (min.) residual electron density 0.35 (−0.25) e Å−3, hydrogen atoms calculated and refined as riding atoms. X-ray crystal structure analysis of 4a: formula C11H22ClN⋅0.5 H2O, M=212.75, colorless crystal 0.35×0.25×0.10 mm, a=12.6801(5), c=13.6253(3) Å, V=1897.24(11) Å3, ρcalc=1.117 g cm−3, μ=2.394 mm−1, empirical absorption correction (0.488≤T≤0.796), Z=6, trigonal, space group P3121 (No. 152), λ=1.54178 Å, T=223(2) K, ω and ϕ scans, 15069 reflections collected (±h, ±k, ±l), [(sinθ)/λ]=0.60 Å−1, 2239 independent (Rint=0.049) and 2169 observed reflections [I≥2σ(I)], 129 refined parameters, R=0.036, wR2=0.098, Flack parameter 0.00(2), max. (min.) residual electron density 0.23 (−0.21) e Å−3, hydrogen atom at O from difference Fourier calculations, others calculated and refined as riding atoms. Data sets were collected with a Nonius KappaCCD diffractometer. Programs used: data collection COLLECT (Nonius B. V., 1998), data reduction Denzo-SMN (, , Methods in Enzymology, 1997, 276, 307–326), absorption correction Denzo (, , , , Acta Crystallogr. 2003, A59, 228–234), structure solution SHELXS-97 (, Acta Crystallogr. 1990, A46, 467–473), structure refinement SHELXL-97 (, Acta Crystallogr. 2008, A64, 112–122), graphics SCHAKAL (E. Keller, Universität Freiburg, 1997).
- 9bCCDC 726206 and 726207 contain 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.
- 10Cleavage of a chiral auxiliary often leaves behind an undesired functional group, whereas in this case, a CH bond is formed on the parent molecule: “traceless cleavage”. The term “traceless cleavage” is usually used in the context of traceless linkers: , , Chem. Eur. J. 2000, 6, 1899.
- 11
- 11a, , , , , , Angew. Chem. 2000, 112, 505;Angew. Chem. Int. Ed. 2000, 39, 495;Direct Link:
- 11b