A redox-neutral, mild, and simple protocol is developed for the synthesis of α-trifluoromethylated ketones from vinyl azides under transition-metal-free conditions. In the presence of organic photoredox catalyst N-methyl-9-mesityl acridinium and sodium trifluoromethanesulfinate, a broad range of substituted vinyl azides were found to react smoothly upon visible-light irradiation, readily furnishing the corresponding products in satisfied yields.

Here we report a novel electron-donor–acceptor (EDA) complex-enabled three-component cyanofluorination of vinyl azides under metal-free conditions in a cis-specific manner. This reaction protocol is operationally simple without exclusion of either moisture or oxygen, allowing access to a wide range of highly-functionalized α-azido-β-fluoronitriles bearing quaternary carbons that are difficult to obtain by existing methods.

A novel protocol is herein described for the preparation of tri-/difluoromethylated N,N-dialkylhydrazones under transition-metal-free conditions and this reaction can be scaled up to the gram level easily. The reaction protocol is operationally simple and performed at ambient temperature, allowing obtaining the desired products in satisfactory yields. The easy-to-handle sodium tri- and difluoromethanesulfinates serve as effective fluoroalkyl radical precursors.

A mild and transition-metal-free protocol is herein presented for the preparation of 6-fluoroalkylphenanthridines and this reaction can be readily scaled up to the gram level. The easy-handling sodium tri-, di-, and monofluoromethanesulfinates are used as efficient radical fluoroalkylation reagents under ambient conditions. In the presence of the organic photoredox catalyst N-methyl-9-mesityl acridinium, a range of desired products were afforded in satisfactory yields upon visible-light irradiation.

A mild and transition-metal-free protocol is herein presented for the preparation of 6-fluoroalkylphenanthridines and this reaction can be readily scaled up to the gram level. The easy-handling sodium tri-, di-, and monofluoromethanesulfinates are used as efficient radical fluoroalkylation reagents under ambient conditions. In the presence of the organic photoredox catalyst N-methyl-9-mesityl acridinium, a range of desired products were afforded in satisfactory yields upon visible-light irradiation.

A mild and transition-metal-free protocol is herein presented for chloro-, bromo- and trifluoromethylthiotrifluoromethylation of unactivated alkenes. The easy-handling Langlois reagent, as well as N-halophthalimide and N-trifluoromethylthiosaccharin, is used in this method. In the presence of an organic photoredox catalyst N-methyl-9-mesityl acridinium, a broad range of desired products were afforded in satisfactory yields upon visible-light irradiation via a radical process.

A metal-free efficient synthesis of olefins via microwave-assisted direct decarboxylative elimination of arylacetic acids is described. This reaction, using commercially available reagent PIFA as oxidant, readily provides a variety of desired products in moderate to good yields.

An efficient and mild fluorination of vinyl azides for the synthesis of α-fluoroketones is described. The mechanistic studies indicated that a single-electron transfer (SET) and a subsequent fluorine atom transfer process could be involved in the reaction.

We report herein a CuX2-mediated halocyclization of γ,δ-unsaturated amides for the synthesis of functionalized iminolactones and lactams respectively under mild reaction conditions. Mechanism studies indicated that N-attack cyclization was via a radical route while oxycyclization was via a nucleophilic attack on the activated CC bond.

A palladium-catalyzed efficient synthesis of 5-methylisoxazoles via oxime-mediated functionalization of unactivated olefins is described. The reaction affords a variety of 5-methylisoxazoles in moderate to good yields. To further demonstrate the utility of the method, the rapid synthesis of valdecoxib and oxacillin is reported.

A concise synthesis of (S)-14-azacamptothecin has been accomplished in 8 steps from commercially available (R)-2-hydroxybutanoic acid. The key strategy involved in this synthesis is the Michael addition/β-elimination sequence to construct the chiral quaternary carbon center, followed by palladium catalyzed cyanation and formal [4 + 2] cycloaddition/elimination/aromatization in a one pot manner to form the pyrrolopyrimidin-4-one moiety.

A concise synthesis of (S)-14-azacamptothecin has been accomplished in 8 steps from commercially available (R)-2-hydroxybutanoic acid. The key strategy involved in this synthesis is the Michael addition/β-elimination sequence to construct the chiral quaternary carbon center, followed by palladium catalyzed cyanation and formal [4 + 2] cycloaddition/elimination/aromatization in a one pot manner to form the pyrrolopyrimidin-4-one moiety.

We report herein a CuX2-mediated halocyclization of γ,δ-unsaturated amides for the synthesis of functionalized iminolactones and lactams respectively under mild reaction conditions. Mechanism studies indicated that N-attack cyclization was via a radical route while oxycyclization was via a nucleophilic attack on the activated CC bond.

A redox-neutral, mild, and simple protocol is developed for the synthesis of α-trifluoromethylated ketones from vinyl azides under transition-metal-free conditions. In the presence of organic photoredox catalyst N-methyl-9-mesityl acridinium and sodium trifluoromethanesulfinate, a broad range of substituted vinyl azides were found to react smoothly upon visible-light irradiation, readily furnishing the corresponding products in satisfied yields.

A mild and transition-metal-free protocol is herein presented for chloro-, bromo- and trifluoromethylthiotrifluoromethylation of unactivated alkenes. The easy-handling Langlois reagent, as well as N-halophthalimide and N-trifluoromethylthiosaccharin, is used in this method. In the presence of an organic photoredox catalyst N-methyl-9-mesityl acridinium, a broad range of desired products were afforded in satisfactory yields upon visible-light irradiation via a radical process.

An efficient Fe(II)-catalyzed trifluoromethylation of vinylcyclopropanes was successfully developed. A series of CF3-containing dihydronaphthalene derivatives were prepared in moderate to high yields (up to 96%) under mild reaction conditions using the Togni reagent as the CF3 source.