Synthesis 2005(2): 334-337  
DOI: 10.1055/s-2004-834864
PSP
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Highly Enantioselective Synthesis of Cyclic Allylic and Homoallylic Alcohols with Dialkylzinc Reagents

Mauro Pineschi*, Federica Del Moro, Paolo Crotti, Valeria Di Bussolo, Franco Macchia
Dipartimento di Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, 56126 Pisa, Italy
Fax: +39(050)2219660; e-Mail: [email protected];
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Publikationsverlauf

Received 27 May 2004
Publikationsdatum:
21. Oktober 2004 (online)

Abstract

The copper-phosphoramidite catalyzed addition of dialkylzinc reagents to racemic or meso allylic epoxides can be synthetically exploited in different ways, depending on the substrates and reaction conditions used.

    References

  • 1 For a recent overview of the copper-catalyzed ring opening reactions of small-ring heterocycles with dialkylzinc reagents, see: Pineschi M. New. J. Chem.  2004,  657 
  • 2a Feringa BL. Pineschi M. Arnold LA. Imbos R. de Vries AHM. Angew. Chem., Int. Ed. Engl.  1997,  36:  2620 
  • 2b Chiral ligand 1 was recently used in the iridium-catalyzed allylic etherification and amination of achiral allylic esters: Ohmura T. Hartwig JF. J. Am. Chem. Soc.  2002,  124:  15164 
  • 2c Also see: Lopez F. Ohmura T. Hartwig JF. J. Am. Chem. Soc.  2003,  125:  3426 
  • ( S,R,R )-Diastereoisomeric phosphoramidite, derived from (S)-BINOL and (R)-bis-phenylethylamine developed by Feringa et al. is to date one of the most effective chiral ligand for several copper-catalyzed enantioselective conjugate additions. For some recent examples, see:
  • 3a Pineschi M. Del Moro F. Gini F. Minnaard AJ. Feringa BL. Chem. Commun.  2004,  1244 
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12

In this case, the use of lower amounts of the chiral catalyst (<1.0 mol%) gave a very sluggish reaction.