Radical trifluoromethylation has been emerging as a versatile tool for the synthesis of trifluoromethylated compounds that play increasingly important roles in pharmaceuticals, agrochemicals and materials science.

The copper-catalyzed intramolecular coupling of aryl bromides with 1,3-dicarbonyls via a six-membered ring closure was examined. With CuI (10 mol %) as the catalyst, N,N'-dimethylethylenediamine as the ligand, and Cs2CO3 as the base, the reactions of alpha-(2-bromobenzyl)-beta-keto esters in THF at refluxing temperature afforded the corresponding substituted 4H-1-benzopyrans in high yields via O-arylation. On the other hand, the reactions of delta-(2-bromophenyl)-beta-keto esters in refluxing dioxane led to the formation of 3,4-dihydronaphthalen-2(1H)-one derivatives via C-arylation.

The chiral TRIP anion combined with a simple commercially available palladacycle furnishes a highly active catalyst for the enantioselective rearrangement of allylic imidates to the corresponding amide products in high yields (see scheme). The stereoselectivity is induced entirely by the chiral phosphate anion although the catalyst complex contains a chiral palladacycle (see scheme).

Platinum(II) salts in combination with copper salts and molecular oxygen catalyse an unprecedented intramolecular transfer of heteroatoms to alkenes to yield aminooxygenation products under sustainable conditions.