A new phosphine-free Co(ii) complex-catalyzed synthesis of various quinoxalines via dehydrogenative coupling of vicinal diols with both o-phenylenediamines and 2-nitroanilines is reported. This complex was also effective for the synthesis of quinolines. The practical aspect of this catalytic system was revealed by the one-pot synthesis of 2-alkylaminoquinolines.

Radical 1,3-trifluoromethylation/alkynylation of various allylboronic esters with concomitant 1,2-boron shift with alkynyl triflones is reported. These chain reactions proceed via CF 3-radical addition to the allylic double bond, and the adduct radical undergoes 1,2-boron migration to give a translocated C-radical that is trapped by the alkynyl triflone. As products, 1,2,3-trisubstituted alkanes with the trifluoromethyl group at position 1 and the alkynyl functionality at position 3 are formed. The valuable boron moiety is retained in the product and is rearranged to position 2. By using trifluoromethanesulfonyl azide as the radical trapping reagent, the cascade provides a 1-trifluoromethyl-3-azidyl-alk-2-ylboronic ester as the product and Michael acceptors as trapping reagents in combination with the Langlois reagent as the CF 3-radical precursor applying photoredox catalysis afford the corresponding 3-alkylated congeners in a three-component process. Further, the stereochemical course of the 1,2-boron migration and the trapping reaction are investigated.

Desaturation of inert aliphatic CÀ H bonds in alkanes to form the corresponding alkenes is challenging. In this communication, a new and practical strategy for remote site-selective desaturation of amides via radical chemistry is reported. The readily installed N-allylsulfonylamide moiety serves as an N radical precursor. Intramolecular 1,5-hydrogen atom transfer from an inert CÀ H bond to the N-radical generates a translocated C-radical which is subsequently oxidized and deprotonated to give the corresponding alkene. The commercially available methanesulfonyl chloride is used as reagent and a Cu/Ag-couple as oxidant. The remote desaturation is realized on different types of unactivated sp 3 -CÀ H bonds. The potential synthetic utility of this method is further demonstrated by the dehydrogenation of natural product derivatives and drugs.

Formal hydroperfluoroalkylation of enones is achieved in a two-step process comprising conjugate hydroboration and subsequent radical perfluoroalkylation. The 1,4-hydroboration of the enone is conducted in the absence of any transition metal catalyst with catecholborane in 1,2-dichloroethane, and the generated boron enolate is in situ α-perfluoroalkylated with a perfluoroalkyl iodide upon blue LED irradiation in the presence of an amine additive. Both reactions proceed under very mild conditions at room temperature.