This review is focused on the recent advances in chemistry of sulfur dioxide fixation through a radical process. Diverse sulfonyl compounds can be obtained efficiently under mild conditions.

Recent advances in the sulfonylation reactions by using inorganic sulfites as source of sulfonyl group are reported. The approaches employing sulfur dioxide surrogates attractive and promising for synthesis compounds since abundant, easily available cheap.

Recent advances in the sulfonylation of alkenes via insertion sulfur dioxide are summarized. The surrogate DABCO·(SO2)2 or inorganic sulfites is used transformation through a radical process. Two strategies for with have been developed. In most cases, vicinal difunctionalization initiated by arylsulfonyl generated situ. Although efficient, asymmetric versions still challenging and less to be explored. It expected that will developed rapidly near future.

Recent advances in the sulfonylation of C-H bonds with insertion sulfur dioxide are summarized. Usually, a surrogate, DABCO·(SO2)2, is used, which avoids utilization gaseous transformation. Inorganic sulfites such as sodium metabisulfite also effective C(sp3)-H bond sulfonylation. under transition metal catalysis or through radical process has been developed. In some cases, can be performed catalyst- and additive-free conditions, facilitated by visible light irradiation. The efficiency...

This review is focused on the recent advances in transition metal-catalyzed direct remote C–H-functionalization of alkyl groups <italic>via</italic> C(sp³)–H bond activation. In general, carboxamide/ester-chelated β-functionalization reactions are summarized.

A novel copper-catalyzed direct trifluoromethylation of internal alkynes was developed, obtaining a series trifluoromethylated coumarins in good yields. The cyclization proposed to proceed via radical mechanism under conditions with functional group tolerance.

A novel and efficient route for the preparation of quinazolin-4(3H)-imines via a palladium-catalyzed three-component reaction carbodiimide, isocyanide, nucleophile is described. The isocyanide insertion believed to be key step during process.

A palladium-catalyzed three-component reaction of bis-(2-iodoaryl)carbodiimide, isocyanide, and amine gives rise to quinazolino[3,2-a]quinazolines related compounds in good yields. Multi-bonds are formed one pot through nucleophilic attack, isocyanide insertion, C–N coupling during the process.

Recent developments in the photochemical carbon–carbon and carbon–heteroatom bond formation via photoinduced Ar–X dissociation are summarized. The transformations through enabled by photoenergy include nucleophilic substitution, arylation, alkylation, aminocarbonylation, aminosulfonylation decarboxylative coupling reactions. Usually, reactions undergo one-electron-transfer couplings aryl radicals or cations involved as key intermediates. Under ultraviolet irradiation visible light, of...

A photoredox-catalyzed sulfonylation of alkyl iodides, sulfur dioxide, and electron-deficient alkenes under mild conditions is achieved. Various functional groups including nitro, halo, acetyl, sufonyl, pyridinyl are all tolerated the photoredox conditions.

Recent advances in nitrene chemistry from acyclic precursors are reviewed this paper.

A photocatalytic annulation cascade of unactivated N-alkene-linked indoles with Langlois' reagent by a radical relay is developed at room temperature under blue LED irradiation. The reaction afforded series tri/difluoromethylated pyrrolo[1,2-a]indoles in moderate to good yields. DFT study suggests that the ascribed rhodamine 6G-induced cyclization involving vinyl addition-radical and hydrogen-atom-abstraction (HAA) processes, interestingly, are applied as fluorescent dyes into fluorescence...

Abstract As valuable building blocks for introducing nitrogen, N ‐imide ylides represent an important class of reactive species and are synthons the synthesis nitrogen‐containing heterocycles that potentially have biological activities. During past decades, tremendous efforts been devoted to tandem processes involving as well their asymmetric applications. In particular, several types ylide‐based reactions established, such CH functionalization, nucleophilic addition, cycloaddition, etc....

A silver-promoted decarboxylative annulation of alkynoates with 2-oxoacetic acids leading to the formation 3-acyl-4-arylcoumarins is reported. The process involves radical acylation, 5-<italic>exo</italic>cyclization, and ester migration.

In the presence of a catalytic amount Pd(OAc)2 and stoichiometric tert-butylamine, reaction propargyl carbonates, isocyanides, alcohols afforded polysubstituted aminopyrroles in good yields. Using water as nucleophile instead alcohol, same provided 1,4-dihydro-6H-furo[3,4-b]pyrrol-6-imines. A triple isocyanide insertion to hypothetic (σ-allenyl)palladium(II) intermediate was involved these ABC3-type multicomponent reactions. The key role tert-butylamine accounted for by its with situ...

A bismuth(<sc>iii</sc>) chloride-mediated three-component reaction of anilines, sulfur dioxide, and trifluoromethanesulfanylamide is reported herein for the efficient synthesis antifungal trifluoromethyl thiolsulphonates with a good scope.

The reaction of allyl ethyl carbonates with isocyanides in the presence a catalytic amount Pd(OAc)2 provided ketenimines through β-hydride elimination imidoylpalladium intermediates. insertion isocyanide into π-allyl Pd complex proceeded via an unusual η1 -allyl species. resulting were hydrolyzed to β,γ-unsaturated carboxamides during purification by flash column chromatography on silica gel or converted situ 1,5-disubstituted tetrazoles [3+2] cycloaddition hydrazoic acid trimethylsilyl azide.

A three-component reaction between 4-substituted Hantzsch esters, DABCO·(SO2)2, and vinyl azides in the presence of photoredox catalysts under visible light irradiation is developed. Substituted esters as radical reservoirs are used sulfur dioxide azides. range (Z)-2-(alkylsulfonyl)-1-arylethen-1-amines obtained moderate to good yields with regioselectivity stereoselectivity. The transformation proceeds efficiently mild conditions a broad scope. plausible mechanism proposed, which involves...

A K₂S₂O₈-mediated tandem radical brominative addition of alkynoates, oxidative spiro-cyclization, and 1,2-migration esters is reported for the synthesis 3-bromocoumarins with high efficiency.

In this work, an unprecedented route is described for the synthesis of 2-amino-4-cyanopyrrole derivatives via palladium-catalyzed reductive isocyanide insertion alkynyl imines. reactions, no external reductant added and plays a dual role as both C1 synthon imidoylation cyano source cyanation. Mechanism studies suggest [4 + 1] cycloaddition, insertion, β-carbon elimination, palladium hydride-based reduction are involved. Moreover, application 2-amine-4-cyanopyrroles cysteine probe realized to...

In this work, by using<italic>N</italic>-methoxybenzamides as efficient acyl nitrene precursors, an iron-catalyzed nitrene/alkyne metalation-based chloramidation is reported for the synthesis of isoindol-5-ones.

Abstract A palladium‐catalyzed reaction of 2‐alkynylaniline, isocyanides, and silver acetate is described, leading to 3‐amidylindoles in moderate good yields. During the process, five new bonds are formed with high efficiency one‐pot procedure.