Subscribe to RSS
DOI: 10.1055/s-0029-1216821
Stereocontrolled Synthesis of 1,3-Amino Alcohols by Reduction of Substituted 2-{1-[(tert-Butylsulfinyl)amino]alkyl}cyclohexanones
Publication History
Publication Date:
14 May 2009 (online)
![](https://www.thieme-connect.de/media/synthesis/200912/lookinside/thumbnails/10.1055-s-0029-1216821-1.jpg)
Abstract
Assembly of diethylzinc, cyclohex-2-en-1-one, and a chiral N-tert-butylsulfinyl imine in the presence of an appropriate phosphoramidite ligand yields a β-sulfinylamino cyclohexanone, which on reduction with sodium borohydride or lithium triethylborohydride provides access to a wide range of enantiomerically pure N-tert-butylsulfinyl 1,3-amino alcohols with five stereogenic centers.
Key words
amino alcohols - ketones - reduction - phosphoramidites - multicomponent reaction - stereoselectivity
- 1
Lait SM.Rankic DA.Keay BA. Chem. Rev. 2007, 107: 767 -
2a
He X.-C.Eliel EL. Tetrahedron 1987, 43: 4979 -
2b
Eliel EL.He X.-C. J. Org. Chem. 1990, 55: 2114 - For selected examples, see:
-
3a
Alberola A.Andrés C.Nieto J.Pedrosa R. Synlett 1990, 763 -
3b
Pedrosa R.Andrés C.Iglesias JM. J. Org. Chem. 2001, 66: 243 -
3c
Pedrosa R.Andrés C.Iglesias JM.Pérez-Encabo A. J. Am. Chem. Soc. 2001, 123: 1817 -
3d
Pedrosa R.Andrés C.Nieto J. J. Org. Chem. 2002, 67: 782 -
3e
Villaplana MJ.Molina P.Arques A.Andrés C.Pedrosa R. Tetrahedron: Asymmetry 2002, 13: 5 -
3f
Pedrosa R.Andrés C.Nieto J.del Pozo S. J. Org. Chem. 2003, 68: 4923 -
3g
Pedrosa R.Andrés C.Nieto J.Rosón C. J. Org. Chem. 2005, 70: 4332 -
3h
Pedrosa R.Sayalero S.Vicente M.Maestro A. J. Org. Chem. 2006, 71: 2177 -
5a
González-Gómez JC.Foubelo F.Yus M. Tetrahedron Lett. 2008, 49: 2343 -
5b
González-Gómez JC.Foubelo F.Yus M. J. Org. Chem. 2009, 74: 2547 - For leading references on the use of ligands L1 and L2, see:
-
6a
Feringa BL.Pineschi M.Arnold LA.Imbos R.de Vries AHM. Angew. Chem., Int. Ed. Engl. 1997, 36: 2620 -
6b
Feringa BL. Acc. Chem. Res. 2000, 33: 346 -
6c
Alexakis A.Benhaim C. Eur. J. Org. Chem. 2002, 3221 -
6d
Alexakis A.Backwall JE.Krause N.Pamies O.Dieguez M. Chem. Rev. 2008, 108: 2796 - 7
De Vries AHM.Meetsma A.Feringa BL. Angew. Chem., Int. Ed. Engl. 1996, 35: 2374 - 9 For conformations of aldols derived
from cyclohexanone, see:
Kitamura M.Nakano K.Miki T.Okada M.Noyori R. J. Am. Chem. Soc. 2001, 123: 8939 - 10
Davis FA.Gaspari PM.Nolt BM.Xu P. J. Org. Chem. 2008, 73: 9619 - 11 Sulfinimines 2 and ent-2 were prepared
from phenylpropanal and (RS)- and (S S)-2-methylpropane-2-sulfinamide
(>99% ee) by using CuSO4 as described
in:
Liu G.Cogan DA.Owens TD.Tang TP.Ellman JA. J. Org. Chem. 1999, 64: 1278 - 12 Phosphoramidites L1,
ent-L1, L2, and ent-L2 were
prepared according the procedure described in:
Polet D.Alexakis A.Tissot-Croset K.Corminboeuf C.Ditrich K. Chem. Eur. J. 2006, 12: 3596 - 14a SAINT Area-Detector Integration Software (Version 6.02A) Siemens Industrial Automation, Inc.; Madison (USA): 1995.
-
14b
Sheldrick GM. SADABS Area-Detector Absorption Correction Göttingen University; Germany: 1996. -
14c
Sheldrick GM. SHELX97 [Includes SHELXS97, SHELXL97 and CIFTAB] - Programs for Crystal Structure Analysis (Release 97-2) Institüt für Anorganische Chemie der Universität; Göttingen (Germany): 1998.
References
Synthetic (-)-pulegone is about ten times more expensive than its natural enantiomer.
8Closely related examples are described in references 5a and 5b; attempts to improve the diastereoselectivity by using an excess of Et2Zn were unsuccessful.
13Crystallographic data (excluding structure
factors) for the structure reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as supplementary publication
no. CCDC 723111. Copies of the data can be obtained free of charge
on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [fax: +44(1223)336033;
e-mail:
deposit@ccdc.cam.ac.uk].