Direct oxidative coupling of thiols and benzylic ethers via C(sp3)-H activation and C-O cleavage to lead thioestersElectronic supplementary information (ESI) available: Spectral data for all the reported compounds. See DOI: 10.1039/c4ob02250e

An unprecedented C-S formation method via direct oxidative C(sp 3 )-H bond functionalization and C-O cleavage of benzylic ethers was developed. Various thioesters including thioester structure containing drug intermediates could be achieved by this convenient, metal and base free method in satisfactory yields. An unprecedented protocol for the synthesis of thioesters via C-H thioesterification and C-O cleavage was developed. This CDC protocol was found convenient and easy-to-handle involving the use of DTBP as the only green oxidant.