Preparation of anti-1,2-Disubstituted Homopropargylic Alcohols by Addition of Allenyl(cyano)cuprates to Aldehydes

Abstract

The generality of the addition of allenyl(cyano)cuprates to aldehydes to afford anti-1,2-disubstituted homopropargylic alcohols was studied. The reaction is general, regardless of the nature of the cyanocuprate, although with alkyl-substituted derivatives the anti selectivity is dependent upon the nature of the aldehyde.

Key words

addition reactions - allenes - cuprates - alkynes - diaste­reoselectivity

References

• 1a Groth U. Kesenheimer C. Neïdhofer J. Synlett  2006,  1859 
• 1b Marshall JA. Chobanian HR. Yanik MM. Org. Lett.  2001,  3:  3369 
• 1c Chemla F. Bernard N. Normant J. Eur. J. Org. Chem.  1999,  2067 ; and references cited therein
• 2a Yamamoto H. In Comprehensive Organic Synthesis   Vol. 2:  Trost BM. Fleming I. Heathcock CH. Pergamon; Oxford: 1991.  p.81 
• 2b Marshall JA. Chem. Rev.  2000,  100:  3163 
• 2c Marshall JA. Gung BW. Grachan ML. In Modern Allene Chemistry   Vol. 1:  Krause N. Hashmi SK. Wiley-VCH; Weinheim: 2004.  Chap. 9. p.493 
• 3a Bernaud F. Vrancken E. Mangeney P. Org. Lett.  2003,  5:  2567 
• 3b Vrancken E. Alouane N. Gérard H. Mangeney P. J. Org. Chem.  2007,  72:  in press; DOI: 10.1021/jo062344z 
• For the synthesis of similar derivatives, see:
• 4a

  Refs.1a, 1c, and 2.

• 4b Marshall JA. Eidam P. Schenck EH.
  J. Org. Chem.  2006,  71:  4840 
• 4c Trost BM. Yand H. Probst GD. J. Am. Chem. Soc.  2004,  126:  48 
• 4d Poisson JF. Normant JF. J. Am. Chem. Soc.  2001,  123:  4639 
• 4e Nakagawa T. Kasatkin A. Sato F. Tetrahedron Lett.  1995,  36:  3207 
• 4f Zweifel G. Hahn G. J. Org. Chem.  1984,  49:  4565 
• 5 Mercier F. Epsztein R. Holand S. Bull. Soc. Chim. Fr.  1972,  690 
• 6 Bernaud F. Vrancken E. Mangeney P. Synlett  2004,  1080 
• 7 Alouane N. Bernaud F. Marrot J. Vrancken E. Mangeney P. Org. Lett.  2005,  7:  5797 
• 8 Ohmiya H. Yorimitsu H. Oshima K. Org. Lett.  2006,  8:  3093 
• 9 Bestmann HJ. Zeibig T. Vostrowsky O. Synthesis  1990,  1039