Selective C-H bond hydroxylation of cyclohexanes in water by supramolecular control

A new approach for selective hydroxylation of non-activated cyclohexanes using dioxirane generated in situ in water through supramolecular control has been developed. Using beta-CD and gamma-CD as the supramolecular hosts, selective hydroxylation of cyclohexane substrates, including trans/cis-1,4-, 1,3- and 1,2-dimethylcyclohexanes and trans/cis-decahydronaphthalene, was achieved in up to 54% yield in water. Furthermore, site-selective C-H bond hydroxylation of (+)-menthol was achieved by obstructing the approach of dioxirane to the C-H bond with higher steric hindrance through inclusion complexation with beta-CD and gamma-CD in water.