Improved and Environmentally Friendly Large-Scale Preparation of Cyclohexadienyl-, Cycloheptadienyl Sulfone and Enantiopure Epoxy Cycloheptyl Sulfones

Abstract

Kilogram-scale amounts of cycloheptadienyl phenylsulfone and cyclohexadienyl phenylsulfone were prepared by one operation in 5 stages with over 50% yield and requiring no purification. A practical and efficient method for the Jacobsen asymmetric epoxidation of 1,3-cycloheptadienyl sulfone is described. The reported method is suitable for large-scale synthesis, does not use halogenated solvents nor does it require chromatography

vinyl sulfone - cycloheptadienyl - cyclohexadienyl - bromination - pyridinium salt - Jacobsen epoxidation

References

<A NAME="RZ01904SS-1">1</A> Torres E. Chen Y. Kim I. Fuchs PL. Angew. Chem. Int. Ed.  2003,  27:  3124 

<A NAME="RZ01904SS-2">2</A> Meyers DJ. Fuchs PL. J. Org. Chem.  2002,  67:  200 

<A NAME="RZ01904SS-3">3</A> Hentemann MF. Fuchs PL. Tetrahedron. Lett.  1997,  38:  5615 

<A NAME="RZ01904SS-4">4</A> Jiang WL. Lantrip DA. Fuchs PL. Org. Lett.  2000,  2:  2181 

<A NAME="RZ01904SS-5">5</A> Labiad B. Villemin D. Synthesis  1989,  143 

<A NAME="Z01904SS-6">6</A>

Polyaniline-sulfuric acid salt gave a similar result to Montmorillonite KSF:

Palaniappan S. Narender P. Saravanan C. Rao VJ. Synlett  2003,  1793 

<A NAME="RZ01904SS-7">7</A> Sels B. Vos D. Buntinx M. Pierard F. Mesmaeker AK. Jacobs P. Nature (London)  1999,  400:  855 

<A NAME="RZ01904SS-8">8</A> Sato K. Hyodo M. Aoki M. Zheng X. Noyori R. Tetrahedron  2001,  57:  2469 

<A NAME="RZ01904SS-9">9</A>

Prepared from Aliquat 336 (Aldrich) according to Noyori’s procedure. [8]

<A NAME="RZ01904SS-10">10</A>

Based on prices from Aldrich catalog, including reagents necessary for purification.

<A NAME="RZ01904SS-11">11</A> Pietikäinen P. Tetrahedron  1998,  54:  4319 

<A NAME="RZ01904SS-12">12</A> Thellend A. Battioni P. Mansuy D. J. Chem. Soc., Chem. Commun.  1994,  1035 

<A NAME="RZ01904SS-13">13</A> Palucki M. Hanson P. Jacobsen EN. Tetrahedron Lett.  1992,  33:  7111 

<A NAME="RZ01904SS-14A">14a</A> Hentemann MF. Fuchs PL. Org. Lett.  1999,  1:  355 

<A NAME="RZ01904SS-14B">14b</A> Hentemann MF. Fuchs PL. Tetrahedron Lett.  1999,  40:  2699 

<A NAME="RZ01904SS-15">15</A> Bäckvall JE. Juntunen SK. Andell OS. Org. Synth.  1989,  68:  148