The regioselective synthesis of 3-phosphinylated coumarins in moderate to excellent yields was developed via an EY/BPO-mediated cross-dehydrogenative coupling (CDC) reaction under green LED irradiation. The results of control experiments showed that the active intermediate, a P-centered radical, might be obtained through energy transfer and electron transfer processes.

Cu-catalyzed CDC reactions of coumarins with cyclic ethers and cycloalkanes were achieved to afford a variety of C-3 functionalized coumarins bearing the C(sp2)–C(sp3) bond in moderate to excellent yields. The conversion was proposed to proceed via a radical process.

A new and efficient metal-free tandem acylation/cyclization of alkynoates with aldehydes was developed for the synthesis of 3-acyl-4-arylcoumarins. The reaction was achieved by the addition of acyl radical to alkynes and a C–H bond functionalization to form two new C–C bonds simultaneously.

An efficient and practical bis(alkoxo)palladium complex Cat.I catalyzed C–H arylation of heterocycles with heteroaryl chlorides has been developed. With 1 mol % of Cat.I, the direct arylation of a series of heterocycles with various heteroaryl chlorides could proceed smoothly affording desired products in moderate to excellent yields. The catalytic system allows one-pot synthesis of 2,5-diheteroaryled thiophenes via twofold direct C–H arylation.

Ag2CO3-catalyzed difunctionalization of alkynes via a radical phosphonation and C–H functionalization tandem process was developed to synthesize various 3-phosphonated coumarins in moderate to high yields with high regioselectivity. A catalytic amount of cheap and nontoxic silver salt was employed in the domino C–P and C–C formation of alkynoates for the first time. Mechanistic studies indicate that the reaction pathway might proceed via the generation and cyclization of a phosphonated vinyl radical intermediate.

Silver-catalyzed carbonphosphonation of α,α-diaryl allylic alcohols is achieved. A series of γ-ketophosphonates with different substituents were readily obtained. The mechanistic study indicated that the reaction was initiated by the addition of P-radicals, which sequentially undergo 1,2-migration of an aryl group to form C(Ar)–C(sp3) bonds.

With good to excellent yields, a series of mono- or diheteroaryl compounds were synthesized via the palladacycle-catalyzed Suzuki–Miyaura reaction of various N-methyliminodiacetic acid (MIDA) boronates with aryl/heteroaryl halides in EtOH/H2O or H2O.

An efficient phosphine-free direct C–H arylation of thiophenes at the α-position has been developed at low catalyst loading of bis(alkoxo)palladium complex (Cat.I, 0.1–0.2 mol %). The developed synthetic method can be applied to the synthesis of α-aryl/heteroaryl thiophenes from aryl or heteroaryl bromides in good to excellent yields and is compatible with the substrates bearing electron-donating or electron-withdrawing groups. The reactivities of the 2- and 5-positions of thiophenes are equivalent and not dependent on steric hindrance under optimal conditions. This condition can also be applied to other heterocyclic moieties such as benzothiophene, benzofuran, and pyrrole with high conversion yields.

A novel Pd(II)-catalyzed dehydrogenative cross-coupling reaction between coumarins and H-phosphonates has been developed to give the corresponding 3-phosphonated products in moderate to good yields with high selectivity.

A novel efficient tandem cyclization–methoxylation reaction has been developed to synthesize cyclopentadienyl alkyl ethers via palladium-catalyzed trimerization of diarylethynes and elimination of one dimethoxymethyl benzene molecule. The reaction mechanism was investigated by the Q-Tof APCI-HRMS technique, and the fluorescent properties of the obtained compounds were studied in the solid state and in solution.

Silver-catalyzed carbonphosphonation of α,α-diaryl allylic alcohols is achieved. A series of γ-ketophosphonates with different substituents were readily obtained. The mechanistic study indicated that the reaction was initiated by the addition of P-radicals, which sequentially undergo 1,2-migration of an aryl group to form C(Ar)–C(sp3) bonds.