Gold-Catalyzed Dehydrative Cyclization of Allylic Diols

Abstract

The gold(I)-catalyzed cyclization of monoallylic diols is an efficient method for the formation of tetrahydropyrans from readily available, easily prepared substrates. The reaction has been shown to be general and high yielding with low catalyst loadings. Several new synthetically useful substrates and efficient methods for both their preparation and cyclization are reported.

allylic diol - dehydrative cyclization - tetrahydropyran - gold-catalysis - cross-metathesis

References

1 For leading references, see: Yeung K.-S. Paterson I. Chem. Rev.  2005,  105:  4237 

2 Blunt JW. Copp BR. Hu W.-P. Munro MHG. Northcote PT. Prinsep MR. Nat. Prod. Rep.  2008,  25:  35 

3 Aponick A. Li C.-Y. Biannic B. Org. Lett.  2008,  10:  669 

For recent reviews on homogeneous Au-catalyzed reactions, see:

4a Muzart J. Tetrahedron  2008,  64:  5815 

4b Shen HC. Tetrahedron  2008,  64:  3885 

4c Hashmi ASK. Chem. Rev.  2007,  107:  3180 

4d Gorin DJ. Toste FD. Nature  2007,  446:  395 

4e Hashmi ASK. Catal. Today  2007,  122:  211 

4f Jiménez-Núñez E. Echavarren AM. Chem. Commun.  2007,  333 

4g Hashmi ASK. Hutchings GJ. Angew. Chem. Int. Ed.  2006,  45:  7896 

4h Hoffmann-Röder A. Krause N. Org. Biomol. Chem.  2005,  3:  387 

5 Chatterjee AK. Choi T.-L. Sanders DP. Grubbs RH. J. Am. Chem. Soc.  2003,  125:  11360 

Similar compounds have previously been prepared by cross-metathesis and from δ-valerolactone. For details, see:

6a Cossy J. BouBouz S. Hoveyda AH. J. Organomet. Chem.  2001,  634:  216 

6b Chen S.-H. Hong B.-C. Su C.-F. Sarshar S. Tetrahedron Lett.  2005,  46:  8899 

7

We find that the most simple and effective workup method for this system involves direct adsorption of the reaction mixture onto silica gel followed immediately by column chromatography.

8 For leading references on metathesis workup procedures, see: Hong SH. Grubbs RH. Org. Lett.  2007,  9:  1955 ; and references cited therein