Inspired by the reaction mechanism of photo-induced DNA cleavage in nature, a C(sp )-H cyanation reaction promoted by visible-light photoredox/phosphate hybrid catalysis was developed. Phosphate radicals, generated by one-electron photooxidation of phosphate salt, functioned as a hydrogen-atom-transfer catalyst to produce nucleophilic carbon radicals from C(sp )-H bonds with a high bond-dissociation energy. The resulting carbon radicals were trapped by a cyano radical source (TsCN) to produce the C-H cyanation products. Due to the high functional-group tolerance and versatility of the cyano group, the reaction will be useful for realizing streamlined building block syntheses and late-stage functionalization of drug-like molecules.

We developed a palladium-catalyzed C−H transformation that enabled the synthesis of ketones from aldehydes and (hetero)aryl halides. The use of picolinamide ligands was key to achieving the transformation. Heteroaryl ketones, as well as diaryl ketones, were synthesized in good to excellent yields, even in gram-scale, using this reaction. Results of density functional theory (DFT) calculations support the C−H bond activation pathway.

We successfully developed an iridium-catalyzed ortho-selective C-H silylation of aromatic compounds. The reaction exhibited a wide substrate scope, and a variety of π-conjugated molecules were synthesized in good to excellent yields, even in gram scale. Several silyl groups could also be introduced into the products. The experimental results indicated that the regioselectivity could be controlled by a Lewis acid-base interaction between the Lewis acidic silicon atoms of fluorinated hydrosilanes and the Lewis basic nitrogen atoms of aromatic compounds.

An efficient method for C7-position-selective alkenylation of N-substituted indolines with alkenes is reported. Various 7-alkenylindolines were obtained in moderate to excellent yields in air in the presence of catalytic amounts of [Cp*IrCl2]2, AgOTf, and Cu(OAc)2. The protocol relies on the use of a carbonyl or carbamoyl group on the nitrogen atom of indoline as a directing group and is potentially applicable to the synthesis of 7-alkenylindoles and 7-alkylindoles.

A catalytic enantioselective proton migration of skipped enynes to allenes is developed. A newly identified chiral ferrocenyl phosphine ligand plays critical roles in controlling both regio-and enantioselectivity. The method offers a new concept to convert readily available and abundant feedstock hydrocarbons into high-value-added molecules by reconstituting C-H bond connectivity without relying on polar functional groups.