trans,anti,trans-Tetra(spirotetrahydrofuranyl)cyclohexane-1,2-dione. Stereocontrolled Synthesis and Definition of Its Susceptibility to Photoisomerization.
The title alpha-diketone (18) has been synthesized in stereocontrolled fashion. The ability to introduce the four contiguous spirocyclic ether oxygens in extended trans fashion rests on the ability of the Normant reagent (ClMgCH(2)CH(2)CH(2)OMgCl) to engage in chelation control during 1,2-addition to an alpha-oxy substituted cyclohexanone. The successful pathway is dependent on the ability of osmium tetraoxide to add (slowly) across the double bond of the cyclohexene precursor. The highly substituted 1,2-cyclohexanedione is quite sensitive to light and rearranges by means of an interesting photoisomerization process to a laterally fused pyran system. A likely mechanistic pathway for this intramolecular isomerization is presented.
Paquette
Leo A.
LA
Evans Chemical Laboratories, The Ohio State University, Columbus, Ohio 43210.
Lowinger
Timothy B.
TB
Bolin
David G.
DG
Branan
Bruce M.
BM