3-Bromopropenyl Methyl Carbonate: A New Reagent for the α-Hydroxy Allylation Reaction of Aldehydes in Water

Abstract

3-Bromopropenyl methyl carbonate reacts smoothly with aldehydes in the presence of zinc in a mixture of saturated aqueous NH₄Cl and THF (9:1). Monoprotected alk-1-en-3,4-diols are formed in high yields and in short reaction times. The reaction is diastereoselective, saturated aldehydes afford anti-adducts, while α,β-unsaturated and aromatic aldehydes preferentially give the syn-isomers. Very simple conditions for the conversion of intermediate monocarbonate derivatives of alk-1-en-3,4-diols to cyclic carbonates are also reported.

zinc - 3-bromopropenyl carbonates - heterosubstituted allyl zinc complexes - water as solvent - monoprotected alk-1-en-3,4-diols

References

1 Pétrier C. Luche J.-L. J. Org. Chem.  1985,  50:  912 

2 Li C.-J. Green Chem.  2002,  4:  1 

3a Lindström UL. Chem. Rev.  2002,  102:  2751 

3b Li CH. Chan TH. Tetrahedron  1999,  55:  11149 

3c Lubineau A. Augé J. Queneau Y. Synthesis  1994,  741 

4a Shaughnessy KH. DeVasher RB. Curr. Org. Chem.  2005,  9:  585 

4b Bai L. Wang J.-X. Curr. Org. Chem.  2005,  9:  535 

5a Kobayashi S. Manabe K. Acc. Chem. Res.  2002,  35:  209 

5b Manabe K. Kobayashi S. Chem.-Eur. J.  2002,  8:  4094 

6 Li C.-J. In Organic Reactions in Aqueous Media   Chan T.-H. Wiley; New York: 1997.  p.199 

7 Breslow R. Acc. Chem. Res.  2004,  37:  471 

8a Girotti R. Lombardo M. Morganti S. Trombini C. Chem. Commun.  2001,  2310 

8b Lombardo M. Morganti S. Trombini C. J. Org. Chem.  2003,  68:  997 

9 Lombardo M. Licciulli S. Trombini C. Pure Appl. Chem.  2004,  76:  657 

10 Dauben HJ. McCoy LL. J. Am. Chem. Soc.  1959,  81:  4863 

11 Minami I. Tsuji J. Tetrahedron  1987,  43:  3903 

12 Jiang S. Agoston GE. Chen T. Cabal MP. Turos E. Organometallics  1995,  14:  4697