A highly chemo- and regioselective [4 + 2] formal cycloaddition of (Z)-3-iodo allylic nucleophiles and allenamides catalyzed by palladium is reported.

An efficient one-pot construction of functionalized 3-methylene-5-phenyl-1,2,3,4-tetrahydropyridine derivatives via palladium-catalyzed cyclization-Heck reaction of allenamides has been described. The 3-methylene-5-phenyl-1,2,3,4-tetrahydropyridine derivatives feature a nonconjugated diene, including one endo-enamine and one exocyclic double bond, which could be used for further transformation. Both aryl and vinyl halides performed very well under the standard conditions, delivering the corresponding products efficiently.

A mild and efficient type of Pd/Cu-catalyzed allenamide allyl acetate reaction with terminal alkynes affording polyfunctionalized 2,3-dihydropyrrole derivatives is reported. Allenamide substrates went through two π-allyl palladium complex processes, and then it was trapped by terminal alkynes on the distal position via a Sonogashira reaction. Two new Csp 3 À Csp 2 and Csp 3 À Csp bonds were efficiently constructed in one pot.

An efficient palladium‐catalyzed direct oxidative esterification reaction of indoles with both aliphatic and aromatic carboxylic acids is reported. The use of Ag2CO3 is crucial to this transformation, as it functions as both a base and an oxidant for the regeneration of the palladium(II) catalyst. This methodology represents a novel prospect for C(sp2)−H acyloxylation and will promote interest in direct C(sp2)−H esterification.

A new type of cascade metallo-ene/Suzuki coupling reaction of allenamides catalyzed by palladium is described. A variety of polyfunctionalized 2,3-dihydropyrrole derivatives, which are important structural motifs for bioactive molecules, were furnished with excellent yields. Two new Csp-Csp bonds were constructed in one pot efficiently. The reductive elimination from π-allyl palladium complex presented excellent regioselectivity to the terminal C1 position. The unique terminal alkene was one of the most easily functionalized groups, providing these molecules with a potential transformation to much more complicated molecules.