A nickel-catalyzed regiosepecific C2- versus C3-oxidative cross-coupling reaction of indoles with 1,4-dioxane and other inactive C­(sp3)–H bonds is described. The divergent synthesis of C­(sp3)–C­(sp2) bonds was achieved in satisfactory yields with di-tert-butyl peroxide (DTBP) as the oxidant, which provides an efficient strategy for the selective construction of cyclic ethers containing heteroaromatic core structures.

Reported herein is a palladium-catalyzed, directed γ-C(sp )-H arylation of protected thiols. The key is to utilize Michael acceptors as a dual reagent to install a protecting/directing group on thiols by a thiol-Michael click reaction, and remove it later under basic conditions. The C-H arylation proceeds with high functional-group tolerance and the deprotected thiols can be further transformed into other sulfur-containing compounds. This unique mode of activation could open the door for site-selective functionalization of thiols or other sulfur-containing compounds at unactivated positions.

Am etal-free C À Cb ondf ormation method via the oxidative cross-coupling reactiono fi sochroman and indole derivatives was established. Various a-fuctionalized cyclic ethers were achieved in satisfactoryy ieldsu sing di-tert-butyl peroxide (DTBP) as the oxidant. This method is also ap otentially effi-cient strategy for the construction of cyclic ethercontainingt argets.

A simple and efficient synthesis of 2-substituted azoles by alkylation of azoles with dicumyl peroxide, methylarenes and cycloalkanes under metal-free condition has been developed.