Collaborative Reduction-Induced Nickel-Catalytic Selective C-S Coupling of Aryl Di/Trithiosulfonates with Aryl Halides.

Metal-catalytic conversion of polysulfide reagents is a major challenge in organic synthesis due to its challenging activation modes of multiple S-S bonds. The utilization of aryl di- and trithiosulfonates in nickel-catalyzed reductive coupling with aryl halides has been unexplored. Herein, we unprecedentedly describe PPh and Zn-collaborative reduction-induced nickel-catalytic selective C-S coupling of aryl di/trithiosulfonates with aryl halides to access sulfides over common disulfides or trisulfides.

Synthetic exploration of electrophilic xanthylation powerful -xanthylphthalimides.

Organic xanthates are broadly applied as synthetic intermediates and bioactive molecules in synthetic chemistry. Electrophilic xanthylation represents a promising approach but has rarely been explored mainly due to the lack of powerful electrophilic reagents. Herein, synthetic exploration of electrophilic xanthylation powerful -xanthylphthalimides was investigated.

Lewis Base-Catalyzed Trifluoromethylsulfinylation of Allylic Alcohols: Stability-Oriented Divergent Synthesis.

A novel strategy is demonstrated for Lewis base-activated trifluoromethylsulfinylation of allylic alcohols. Controllable synthesis of structurally varied allylic trifluoromethanesulfones via sigmatropic rearrangements was performed, and trifluoromethanesulfinate esters were achieved. This metal-free, catalytic divergent transformation features good functional group tolerance and late-stage modification of bioactive molecules.

Two-in-one strategy for fluorene-based spirocycles Pd(0)-catalyzed spiroannulation of -iodobiaryls with bromonaphthols.

Rapid assembly of fluorene-based spirocycles represents a highly significant but challenging task in organic synthesis. Reported herein is a novel Pd(0)-catalyzed [4+1] spiroannulation of simple -iodobiaryls with bromonaphthols for the one-step construction of [4,5]-spirofluorenes in high yields with excellent functional group tolerance. Noteworthily, these valuable fluorene-based coumarin skeletons can enrich the database of -coumarins and exhibit excellent spectroscopic properties.

Nickel-Catalyzed Cross-Coupling of Umpolung Carbonyls and Alkyl Halides.

An effective nickel-catalyzed cross-coupling of Umpolung carbonyls and alkyl halides was developed. Complementary to classical alkylation techniques, this reaction utilizes Umpolung carbonyls as the environmentally benign alkyl nucleophiles, providing an efficient and selective catalytic alternative to the traditional use of highly reactive alkyl organometallic reagents.

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel.

Alkenes are fundamental functionalities in nature and highly useful intermediates in organic synthesis, medicinal chemistry and material sciences. Transition-metal-catalyzed Heck couplings with organic halides as electrophiles have been established as a powerful protocol for the synthesis of this valuable building block. However, the requirement of organic halides and the generation of stoichiometric hazardous halide wastes may cause significant sustainable concerns.

Umpolung of Carbonyl Groups as Alkyl Organometallic Reagent Surrogates for Palladium-Catalyzed Allylic Alkylation.

Palladium-catalyzed allylic alkylation of nonstabilized carbon nucleophiles is difficult and remains a major challenge. Reported here is a highly chemo- and regioselective direct palladium-catalyzed C-allylation of hydrazones, generated from carbonyls, as a source of umpolung unstabilized alkyl carbanions and surrogates of alkyl organometallic reagents. Contrary to classical allylation techniques, this umpolung reaction utilizes hydrazones prepared not only from aryl aldehydes but also from alkyl aldehydes and ketones as renewable feedstocks.

Radical difluoromethylthiolation of aromatics enabled by visible light.

Direct introduction of a difluoromethylthio group (-SCFH) to arenes represents an efficient route to access a valuable catalogue of organofluorines; however, to realize this transformation under metal-free and mild conditions still remains challenging and rarely reported. Herein, a metal-catalyst-free and redox-neutral innate difluoromethylthiolation method with a shelf-stable and readily available reagent, PhSOSCFH, under visible light irradiation is described. This light-mediated protocol successfully converts a broad spectrum of arenes and heteroarenes to difluoromethylthioethers in the absence of noble metals and stoichiometric amounts of additives.

Iron-Catalyzed Nucleophilic Addition Reaction of Organic Carbanion Equivalents via Hydrazones.

Earth-abundant and well-defined iron complexes are found to be cheap and effective catalysts for a series of " umpolung" nucleophilic additions of hydrazones. The new catalytic system not only maintains the broad substrate scope of an earlier expensive ruthenium system but also attains chemoselectivity of different kinds of carbonyl groups. Furthermore, the iron catalyst enables this reaction at ambient temperature.

PhSO SCF H: A Shelf-Stable, Easily Scalable Reagent for Radical Difluoromethylthiolation.

A new shelf-stable and easily scalable difluoromethylthiolating reagent S-(difluoromethyl) benzenesulfonothioate (PhSO SCF H) was developed. PhSO SCF H is a powerful reagent for radical difluoromethylthiolation of aryl and alkyl boronic acids, decarboxylative difluoromethylthiolation of aliphatic acids, and a phenylsulfonyl-difluoromethylthio difunctionalization of alkenes under mild reaction conditions.

Silver-catalyzed decarboxylative trifluoromethylthiolation of aliphatic carboxylic acids in aqueous emulsion.

A silver-catalyzed decarboxylative trifluoromethylthiolation of secondary and tertiary carboxylic acids under mild conditions tolerates a wide range of functional groups. The reaction was dramatically accelerated by its performance in an aqueous emulsion, which was formed by the addition of sodium dodecyl sulfate to water. It was proposed that the radical, which was generated from the silver-catalyzed decarboxylation in the "oil-in-water" droplets, could easily react with the trifluoromethylthiolating reagent to form the product.