Practical One-Step Synthesis of Koga’s Chiral Bases

Abstract

A simple, efficient and practical method for the preparation of Koga"s chiral bases is described. The method involves attack of an amine on a styrene oxide-derived aziridinium ion and has allowed the synthesis of novel diamines which cannot be prepared using Koga"s original route.

Key words

amines - chirality - amino alcohols - aziridinium ions

References

• 1 For a review, see: O"Brien P. J. Chem. Soc., Perkin Trans. 1  1998,  1439 
• For recent examples, see:
• 2a Majewski M. Ulaczyk A. Wang F. Tetrahedron Lett.  1999,  40:  8755 
• 2b de Sousa SE. O"Brien P. Steffens HC. Tetrahedron Lett.  1999,  40:  8423 
• 2c Aggarwal VK. Humphries PS. Fenwick A. Angew. Chem. Int. Ed.  1999,  38:  1985 
• 2d Asami M. Ogawa M. Inoue S. Tetrahedron Lett.  1999,  40:  1563 
• 2e Södergen MJ. Andersson PG. J. Am. Chem. Soc.  1998,  120:  10760 
• 2f Södergen MJ. Bertilsson SK. Andersson PG. J. Am. Chem. Soc.  2000,  122:  6610 
• 2g Clayden J. Johnson P. Penk JH. J. Chem. Soc., Perkin Trans 1  2001,  371 
• 3 Cain CM. Cousins RPC. Coumbarides G. Simpkins NS. Tetrahedron  1990,  46:  523 
• 4a Shirai R. Tanaka M. Koga K. J. Am. Chem. Soc.  1986,  108:  543 
• 4b Shirai R. Sato D. Aoki K. Tanaka M. Kawasaki H. Koga K. Tetrahedron  1997,  53:  5963 
• 5 Shirai R. Aoki K. Sato D. Kim HD. Murakata M. Yasukata T. Koga K. Chem. Pharm. Bull.  1994,  42:  690 
• 6a Smith AB. Nolen EG. Shirai R. Blase FR. Ohta M. Chida N. Hartz RA. Fitch DM. Clark WM. Sprengler PA. J. Org. Chem.  1995,  60:  7837 
• 6b MaGee DI. Setiadji S. Martin RA. Tetrahedron: Asymmetry  1995,  6:  639 
• 6c Momose T. Toshima M. Seki S. Koike Y. Toyooka N. Hirai Y. J. Chem. Soc., Perkin Trans. 1  1997,  1315 
• 6d Majewski M. Lazny R. Tetrahedron Lett.  1994,  35:  3653 
• 7 Saravanan P. Singh VK. Tetrahedron Lett.  1998,  39:  167 
• 8 de Sousa SE. O"Brien P. Poumellec P. J. Chem. Soc., Perkin Trans. 1  1998,  1483 
• 10 Meister W. Guthrie RD. Maxwell JL. Jaeger DA. Cram DJ. J. Am. Chem. Soc.  1969,  91:  4452 
• 11 Murakata M. Nakajima M. Koga K. J. Chem. Soc., Chem. Commun.  1990,  1657 
• 12 Jain ASG. Huang SG. Whitesides GM. J. Am. Chem. Soc.  1994,  116:  5057 
• 13 Yamishita Y. Odashima K. Koga K. Tetrahedron Lett.  1999,  40:  2803 
• 14 Yamashita Y. Emura Y. Odashima K. Koga K. Tetrahedron Lett.  2000,  41:  209 

9

The enantiomeric excess of diamine (R)-2 was established as 95% ee using ¹H NMR spectroscopy in the presence of a chiral shift reagent, (R)-2,2,2-trifluoro-1-(9-anthryl)ethanol.