A convenient photoredox‐catalyzed defluorinative trifluoromethylation of α‐trifluoromethyl alkenes and gem‐difluoroalkenes is developed. The reactions proceeded efficiently via trifluoromethyl radical addition followed by β‐fluorine elimination process, providing a new entry to multifluorinated alkenes in moderate to good yields with excellent stereoselectivity.magnified image

A radical-type copper(i)-catalyzed direct trifluoromethylation of styrene derivatives using CF3SO2Na as a trifluoromethylating source for accessing trifluoromethylated alkenes has been developed.

A reaction protocol in which FeCl and tert-butyl hydroperoxide facilitated a selective radical coupling reaction of aryl alkenes or 1,3-enynes with tert-butyl hydroperoxide and formamides to prepare an array of β-peroxy amides has been achieved. The β-peroxy amide could serve as a synthetic precursor which was facilely converted to β-hydroxy amide, β-keto amide and β-lactam following subsequent chemical transformation.

An efficient and general copper(I)-catalyzed method for the synthesis of multi-substituted vinylsilanes is reported. Multi-substituted allenes with electron-withdrawing groups and propiolate derivatives reacted well with (dimethylphenylsilyl)boronic acid pinacol ester to afford silyl-substituted butenoate derivatives and β-silyl-substituted acrylate derivatives, respectively. The corresponding products could be obtained in moderate to high yields and with good to excellent stereoselectivities.