A palladium-catalyzed regioselective aryl phenoxylation of allenamide with phenol derivatives has been developed, providing valuable branched allyl ether products in moderate to excellent yields under mild reaction conditions. Importantly, only the proximal addition products of allenamide were observed in the reaction process, and no distal addition products were observed. A coordinated palladium complex was proposed to be responsible for the excellent proximal addition in the insertion step. The final nucleophilic attack at a-position was induced by the steric effect of palladium complex.

The octahydro-1H-cyclopenta[c]pyridine skeletons exist in a broad spectrum of bioactive natural products, and the development of efficient and convenient protocols to construct this skeleton remains a challenging task.

In regiodivergent arylamination/aryloxygenation of allenamides, use of Cy 2 NMe caused 2,1-arylamination and the corresponding alkenes were formed with excellent Z configuration. Whereas, utilizing Ag 2 CO 3 caused 2,3-aryloxygenation via an unexpected CO 2 insertion from Ag 2 CO 3 .

A palladium/norbornene cooperative catalyzed selective C-H bond amination of aryl iodides was explored, providing an efficient tool for constructing benzocyclic molecules. When ortho-substituted iodobenzene was involved, the C-H bond amination and following Heck cyclization efficiently delivered a 3-methyl-indole scaffold. On the other hand, we realized the controllable synthesis of monoaminated benzo-cyclobutanyl scaffold. The possible coordination of an installed terminal alkenyl group with palladium and steric hindrance were proposed to be responsible for the monoamination selectivity.

A novel and convenient palladium-catalyzed cascade 5-exo-trig radical cyclization/aromatic C-H alkylation with unactivated alkyl iodides has been described. This strategy provides an efficient access to a variety of 3a-methyl-1,2,3,3a,4,8b-hexahydroindeno[1,2-b]pyrrole derivatives, which facilitate access to a series of medically important heterocyclic bioactive molecules. This protocol involves mild catalytic reaction conditions and shows high functional group tolerance with high stereoselectivity. Mechanistic investigations reveal that an alkyl radical pathway is involved in this reaction.

A highly efficient palladium‐catalyzed cascade metallo‐ene/metallo‐carbene coupling reaction was developed to produce 2,3‐dihydropyrrole derivatives in high yields. In this transformation, two new Csp3−Csp2 and Csp2−Csp2 bonds were constructed in one‐pot. The alkene was one of the most easily functionalized groups, making it possible for these molecules to be transformed into more complex molecules. More importantly, the final product possessed an attractive 1,3,8‐trienes scaffold, which was difficult to be synthesized.