Photodriven Radical Perfluoroalkylation-Thiolation of Unactivated Alkenes Enabled by Electron Donor-Acceptor Complex.

A clean and direct three-component radical 1,2-difunctionalization of various alkenes with perfluoroalkyl iodides and thiosulfonates enabled by the electron donor-acceptor complex has been developed under light illumination at room temperature. The approach offers a convenient and environmentally friendly route for the simultaneous incorporation of Csp3-Rf and Csp3-S bonds, affording valuable polyfunctionalized alkane derivatives containing fluorine and sulfur in satisfactory yields. Consequently, this methodology holds significant value and practicality in the field of organic synthesis.

Metal-free synthesis of 1,3-dichloro-1,5-diarylpentan-5-ones via cascade oxidative radical addition of styrenes with CHCl3.

A novel and efficient metal-free cascade oxidative radical addition of styrenes is developed for the construction of 1,3-dichloro-1,5-diarylpentan-5-ones. This protocol presents a practical one-pot procedure that delivers highly functionalized 1,3-dichloro-1,5-diarylpentan-5-ones in moderate-to-good yields with a broad substrate scope under mild conditions.

The palladium-catalyzed direct C3-cyanation of indoles using acetonitrile as the cyanide source.

The ligand-free palladium-catalyzed C3-cyanation of indoles via direct C-H functionalization was achieved. This protocol, utilizing CH3CN as a green and readily available cyanide source, produced the desired products in moderate to good yields through transition-metal-catalyzed C-CN bond cleavage.

Weak coordinated nitrogen functionality enabled regioselective C-H alkynylation via Pd(II)/mono-N-protected amino acid catalysis.

The exploration of weak coordinated amine derivative enabled regioselective C-H functionalization remains challenging due to the elusive achievement of reactivity and selectivity simultaneously. Herein, regioselective C-H alkynylation of various readily transformable nitrogen functionalities was developed with great efficiency, with the assistance of the mono-N-protected amino acid (MPAA) ligand via Pd(ii) catalysis proceeding via 5, 6 and 7-membered palladacycle intermediates.

Copper-catalyzed oxidative multicomponent reaction: synthesis of imidazo fused heterocycles with molecular oxygen.

An oxidative cascade that involves multicomponent reaction comprising a terminal alkyne, 2-amino N-heterocycle, benzyl or allylic bromide with molecular oxygen, delivering densely functionalized imidazo fused heterocycles, is described. This reaction features a cheap catalyst, a green oxidant, and readily available starting materials, which make the overall synthesis applicable in the quick access to relevant pharmaceutical molecules with imidazole derived heterocycles.

Synthesis of Polysubstituted 3-Amino Pyrroles via Palladium-Catalyzed Multicomponent Reaction.

A novel approach for the synthesis of polysubstituted 3-amino pyrroles via palladium-catalyzed three-component tandem reaction was developed. The procedure constructs various polysubstituted 3-amino pyrroles with moderate to excellent yields under mild reaction conditions with assembly efficiency, readily available starting materials, and good functional group tolerance. Furthermore, this process was successfully applied to the synthesis of different 3-phenyl-1,4-dihydropyrrolo[3,2-b]indole derivatives via an intramolecular Buchwald-Hartwig cross-coupling reaction in two steps.

Assembly of Polysubstituted Maleimides via Palladium-Catalyzed Cyclization Reaction of Alkynes with Isocyanides.

An efficient and convenient palladium-catalyzed cyclization reaction of alkynes with isocyanides is described herein. This protocol allows the practical synthesis of many valuable polysubstituted maleimide derivatives after hydrolysis with a broad scope of substrates and mild reaction conditions. C-C, C═O, and C-N bonds were constructed in this transformation with isocyanide serving as both C and N sources.

Palladium-catalyzed selective aminoamidation and aminocyanation of alkenes using isonitrile as amide and cyanide sources.

A mild and efficient palladium-catalyzed intermolecular aminoamidation and aminocyanation reaction of alkenes with a broad substrate scope has been developed. This cyclization process provides a valuable synthetic tool for obtaining substituted indolines, tetrahydroisoquinolines and pyrrolidines in good to excellent yields.

An efficient synthesis of 2,5-diimino-furans via Pd-catalyzed cyclization of bromoacrylamides and isocyanides.

A novel palladium-catalyzed cyclization of bromoacrylamides with isocyanides gives substituted 2,5-diimino-furans, which can be used as the precursor of maleamides. This synthesis likely proceeds, after isonitrile insertion into C­Pd(II) bond, through the coordination of the amide oxygen atom to the Pd(II) centre as a key step.

Palladium-catalyzed intermolecular aerobic oxidative cyclization of 2-ethynylanilines with isocyanides: regioselective synthesis of 4-halo-2-aminoquinolines.

A robust and regioselective palladium-catalyzed intermolecular aerobic oxidative cyclization of 2-ethynylanilines with isocyanides to the synthesis of 4-halo-2-aminoquinolines is reported herein. The procedure constructs various 4-halo-2-aminoquinolines with moderate to excellent yields (47-94%) and broad substrates scope. Furthermore, this process can be easily extended to synthesis of various 6H-indolo[2,3-b]quinolines via an intramolecular Buchwald-Hartwig cross-coupling reaction in two-step one-pot manner.

Synthesis of 2-aminobenzoxazoles and 3-aminobenzoxazines via palladium-catalyzed aerobic oxidation of o-aminophenols with isocyanides.

A Pd-catalyzed aerobic oxidation of o-aminophenols and isocyanides for the synthesis of 2-aminobenzoxazoles and 3-aminobenzoxazines has been achieved in an air atmosphere. The procedure constructs 2-aminobenzoxazoles and 3-aminobenzoxazines with moderate to excellent yields and a broad substrate scope. Apart from experimental simplicity, this methodology has the advantages of mild reaction conditions and easily accessible starting materials. Furthermore, the utility of this method has also been successfully applied to the synthesis of other types of useful nitrogen heterocycles.

Palladium-catalyzed tandem reaction of o-aminophenols, bromoalkynes and isocyanides to give 4-amine-benzo[b][1,4]oxazepines.

A robust route to 4-amine-benzo[b][1,4]oxazepines relying upon a palladium-catalyzed tandem reaction of o-aminophenols, bromoalkynes and isocyanides has been developed. This chemistry presumably proceeds through the migratory insertion of isocyanides into the vinyl-palladium intermediate as a key step.

Pd-catalyzed and CsF-promoted reaction of bromoalkynes with isocyanides: regioselective synthesis of substituted 5-iminopyrrolones.

The palladium-catalyzed and CsF-promoted annulation reaction of bromoalkynes and isocyanides regioselectively affords a diverse set of 5-iminopyrrolone derivatives. This chemistry presumably proceeds through the bromoacrylamide intermediates, which can be readily prepared from the nucleophilic addition reaction of isocyanides to bromoalkynes in the presence of CsF.

Synthesis of amides via palladium-catalyzed amidation of aryl halides.

A new and efficient method for the synthesis of amides via palladium-catalyzed C-C coupling of aryl halides with isocyanides is reported, by which a series of amides were formed from readily available starting materials under mild conditions. This transformation could extend its use to the synthesis of natural products and significant pharmaceuticals.