Ring contraction/transannular cyclization of chiral bicyclo[3.3.1]nonanediones mediated by thallium(III) nitrate

The reaction of several chiral bicyclo[3.3.1]nonane ketones mediated by thallium(III) nitrate to afford ring contraction products is investigated. The effect of solvent on the oxidation is discussed, and the use of thallium(III) nitrate for the oxidative rearrangement of regioisomers of bicyclononanones is outlined. In compounds with proximately located carbonyl groups in the bicyclic framework, unexpected transannular ring closure was observed.