A concise thiolation of C(sp3)–H bond of cycloalkanes with diaryl disulfides in the presence of oxidant of di-tert-butylperoxide (DTBP) has been developed. This reaction without using any of metal catalyst, tolerates varieties of disulfides and cycloalkanes substrates, giving good to excellent chemical yields, which provides a useful approach to cycloalkyl aryl sulfides from unactivated cycloalkanes.

An iron-catalyzed oxidative esterification reaction between unactivated C(sp(3))-H bonds from symmetric and asymmetric ethers and carboxylic acids using di-tert-butyl peroxide (DTBP) as the oxidant via a cross dehydrogenative coupling (CDC) reaction was established, which tolerates a wide range of cyclic ether substrates to react with aromatic acids and phenylacetic acid, providing an efficient method for the preparation of α-acyloxy ethers with good to excellent yields. Intermolecular competing kinetic isotope effect (KIE) experiments were also carried out, which indicate that C(sp(3))-H bond cleavage may be the rate-determining step of this CDC reaction.

Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.

A metal-free oxidative C(sp(3))-H bond functionalization and subsequent conjugate addition reaction using di-tert-butyl peroxide (DTBP) as the oxidant was established, which tolerates a wide range of simple alkane substrates to react with different substituted chromones for direct preparation of 2-alkylchromanones.

A concise metal-free method for synthesizing 6-alkylthiophenanthridines from 2-isocyanobiaryls and disulfides proceeding through thiolation of isocyanides and intramolecular radical aromatic cyclization is reported.