Nickel-catalysed highly regioselective synthesis of ß-acyl naphthalenes under reductive conditions.

Over the past decade, significant progress has been made in the direct C-H acylation of naphthalenes, occurring at the α or ß-positions to yield valuable ketones through Friedel-Crafts acylation or transition-metal-catalysed carbonylative coupling reactions. Nevertheless, highly regioselective acylation of naphthalenes remains a formidable challenge. Herein, we developed a nickel-catalysed reductive ring-opening reaction of 7-oxabenzonorbornadienes with acyl chlorides as the electrophilic coupling partner, providing a new method for the exclusive preparation of ß-acyl naphthalenes.

Nickel-catalysed chelation-assisted reductive defluorinative sulfenylation of trifluoropropionic acid derivatives.

Herein we reported a directing-group assisted strategy for nickel-catalysed reductive defluorinative sulfenylation of trifluoropropionic acid derivatives with disulfides in the presence of Zn, involving triple C-F bond cleavage. This process yielded a diverse array of carbonyl-sulfide di-substituted alkenes in moderate to good yields with good functional group tolerance. Specifically, the reactions exhibited high E-selectivity with E/Z ratio up to >99 : 1.

Iron-catalysed reductive coupling for the synthesis of polyfluorinated compounds.

Herein we reported the use of Earth-abundant iron as the catalytic metal in the presence of Mn to induce difluorobromoacetates to form carbon radicals, which reacted with trifluoromethyl olefins followed by ß-F elimination to generate the corresponding gem-difluoroolefins. The cross-electrophile coupling displayed excellent functional group tolerance and broad substrate scope under mild reductive conditions, affording a large number of polyfluorinated compounds, which could be further transformed to other valuable molecules.