A simple and efficient method is developed for Pd-catalyzed ortho-acetoxylation using organophosphates, namely, benzylic phosphonic and aryl phosphoric monoacids, as the directing group.

A highly efficient Pd-catalyzed ortho-alkenylation is reported using a mono-phosphoric acid-directing group for the first time. This phosphoric acid-directing group is successfully utilized for the synthesis of various alkenylated products and offers a new approach to transition-metal-catalyzed C-H activation.

A cheap, simple, and effective FeCl(3)-catalyzed Conia-ene cyclization of 2-alkynic 1,3-dicarbonyl compounds was stereospecific to afford alkylidenecyclopentanes in (E)-isomers via the 5-exo-dig pathway. The 5-endo-dig and 6-exo-dig cyclizations were also possible, depending on the structure of the substrates.

Functionalized biaryl compounds were successfully synthesized using phosphates as the ortho-directing group in the Pd(II)/Pd(IV) catalytic cycle.

Fe(OTf) 3 -catalyzed reaction of benzylic acetates with allyltrimethylsilane, azidotrimethylsilane, and cyanotrimethylsilane afforded the corresponding allylated, azido, and cyano products in high yields. 2-Trimethylsilyl-substituted benzofuran and indole worked well to furnish the benzyl-substituted benzofuran and indoles.