Copper-catalyzed fluoroalkylation of alkynes and alkynyl carboxylic acids has been achieved with high functional-group tolerance and excellent regio- and stereoselectivities. A variety of fluoroalkyl halides including ethyl bromodifluoroacetate can be employed. Additionally, an unprecedented decarboxylative fluoroalkylation of α, β-unsaturated carboxylic acids has been achieved via a radical pathway.

An investigation into the regiochemistry of radical functionalization of indoles using cycloalkanes through di-tert-butyl peroxide (DTBP)-promoted C(sp3)–H activation was conducted. A wide range of indoles bearing substituents at different positions was functionalized directly with simple cycloalkanes in moderate to high regioselectivity. 2-, 4- and 7-positions were mainly functionalized.

A selective and facile trifluoromethylation process for a wide range of thiophenols and thiols under metal free conditions has been developed using two simple and safe solids, sodium trifluoro-methanesulfinate and iodine pentoxide, via the radical process.

An operationally simple and selective method for the direct conversion of benzylic C–H to C–F to obtain mono- and difluoromethylated arenes using Selectfluor™ as a fluorine source is developed. Persulfate can be used to selectively activate benzylic hydrogen atoms toward C–F bond formation without the aid of transition metal catalysts.

A fluorous hydrazine-carbothioate organocatalyst was prepared. Together with NCS, the catalyst showed a good activity in acetalization of aldehydes and alcohols. It could be recovered from the reaction mixture by fluorous solid-phase extraction (F-SPE) with excellent purity for direct reuse.

A new fluorous imine carbothioate has been prepared as an organocatalyst for the synthesis of pyrrol-2-ones via the cyclo-condensation reaction of aldehydes, amines, and pyruvate at room temperature. The fluorous catalyst can be easily recovered from the reaction mixture by simple fluorous solid-phase extraction (F-SPE) and used for next run reaction without further purification.

A simple and convenient tandem reaction of α-ketoesters with primary or secondary aromatic amines for the synthesis of polysubstituted 1,2-dihydroquinolines has been developed. The catalytic system (fluorous hydrazine-1,2-bis(carbothioate)/NCS) of the reaction has the advantages of operational simplicity, high efficiency, as well as easy recyclability.

A new fluoroalkylated 1,4-disubstituted [1,2,3]-triazole was prepared and acted as an organocatalyst for aldol condensation of different ketones with various aldehydes. Aldol condensation proceeded efficiently in the presence of catalytic amount of fluoroalkylated [1,2,3]-triazole. The catalyst could be easily recovered by fluorous solid-phase extraction with excellent purity and reused for three runs with slightly decrease in its activity.Fluoroalkylated 1,4-disubstituted [1,2,3]-triazole catalyzed aldol condensation of different ketones with different aldehydes to give various α,β-unsaturated ketones in good yields.

The synthesis of 1,5-benzodiazepine derivatives was smoothly carried out in a fluorous aqueous emulsion system composed of perfluorooctane (C8F18) and potassium perfluorooctanesulfonate (C8F17SO3K, KFOS) at room temperature. The aqueous perfluorinated emulsion can be recovered and used again without a significant loss of efficiency.The synthesis of 1,5-benzodiazepine derivatives was smoothly carried out in a fluorous aqueous system composed of perfluorooctane (C8F18) and potassium perfluorooctanesulfonate (C8F17SO3K, KFOS) at room temperature. The aqueous perfluorinated emulsion can be recovered by simple extraction and used again without a significant loss of efficiency.

Aldol condensation of different ketones with various aromatic aldehydes proceeds efficiently in the presence of catalytic amount of perfluoroalkylated-pyridine in a fluorous biphasic system without fluorous solvent, which has prompted various concerns involving cost, solvent leaching, and environmental persistence. The catalyst can be recovered by simple cooling and precipitation and used again.Aldol condensation proceeds efficiently in the presence of catalytic amount of perfluoroalkylated-pyridine under homogeneous conditions in n-octane at 80 °C. The catalyst can be recovered by simple liquid/solid phase separation at 0 °C in the absence of fluorous solvent.

A new fluoroalkylated 1,4-disubstituted [1,2,3]-triazole was prepared and acted as an efficient ligand in the palladium-catalyzed Suzuki–Miyaura coupling reactions of aryl boronic acids and aryl halides (Ar–Br and Ar–Cl) and Mizoroki–Heck reactions of aryl halides and alkenes. All reactions proceeded smoothly to give the desired products in moderate to excellent yields under the optimal conditions. Moreover, the ligand could be easily recovered by fluorous solid-phase extraction with excellent purity and reused with slightly decrease in its activity.Download full-size imageHighlights► A new fluorous triazole ligand was synthesized. ► It displayed excellent catalytic performance in coupling reactions with Pd(OAc)2. ► It could be easily recovered by fluorous solid-phase extraction with good purity. ► It could be reused with slightly decrease in its activity.

An investigation into the regiochemistry of radical functionalization of indoles using cycloalkanes through di-tert-butyl peroxide (DTBP)-promoted C(sp3)–H activation was conducted. A wide range of indoles bearing substituents at different positions was functionalized directly with simple cycloalkanes in moderate to high regioselectivity. 2-, 4- and 7-positions were mainly functionalized.

A selective and facile trifluoromethylation process for a wide range of thiophenols and thiols under metal free conditions has been developed using two simple and safe solids, sodium trifluoro-methanesulfinate and iodine pentoxide, via the radical process.

An operationally simple and selective method for the direct conversion of benzylic C–H to C–F to obtain mono- and difluoromethylated arenes using Selectfluor™ as a fluorine source is developed. Persulfate can be used to selectively activate benzylic hydrogen atoms toward C–F bond formation without the aid of transition metal catalysts.

Copper-catalyzed fluoroalkylation of alkynes and alkynyl carboxylic acids has been achieved with high functional-group tolerance and excellent regio- and stereoselectivities. A variety of fluoroalkyl halides including ethyl bromodifluoroacetate can be employed. Additionally, an unprecedented decarboxylative fluoroalkylation of α, β-unsaturated carboxylic acids has been achieved via a radical pathway.