Described herein is the development of an iron-catalyzed HAT induced radical cyclization hydro-oximation of 1,6-enynes. This transformation involves four step cascade processes: (i) iron-catalyzed hydrogen-atom transfer, (ii) intramolecular radical cyclization of the alkyne, (iii) NO radical capture by the vinyl radical, and (iv) tautomerization of a nitroso alkene to access the ketoximes. Detailed DFT calculations have provided evidence for the transformation processes and the stereoselective formation of ketoximes. Notably, the same strategy has also been applied for the synthesis of pyrrolo[3,2-d]isoxazoles with a quaternary stereocenter via a two-step transformation.

We reported a facile metal-free conversion of aryl halides to the corresponding boronic esters catalysed by an in situ formed donor–acceptor complex. A two-step one-pot method was also developed for site selective aromatic C–H bond borylation.

Facilitated by electron donor–acceptor complexes, an efficient dehydrogenative β-trifluoromethylthiolation of tertiary amines with N-trifluoromethylthiophthalimide is presented under transition-metal-free, external oxidant-free, photocatalyst-free and mild reaction conditions. This protocol accommodates a range of substituted piperidines, as well as seven- and eight-membered saturated heterocycles. Additionally, employing this photocatalyst-free approach, direct β-trifluoromethylthiolation of electron-rich enamides was also achieved through the involvement of a photoactive electron donor–acceptor (EDA) complex.