Oxidant-Assisted Sulfonylation/Cyclization Cascade Synthesis of Alkylsulfonylated Oxindoles via the Insertion of SO2.

An oxidant-assisted tandem sulfonylation/cyclization of electron-deficient alkenes with 4-alkyl-substituted Hantzsch esters and Na2S2O5 for the preparation of 3-alkylsulfonylated oxindoles under mild conditions in the absence of a photocatalyst and transition metal catalyst is established. The mechanism studies show that the alkyl radicals, which come from the cleavage of the C-C bond in 4-substituted Hantzsch esters under oxidant conditions, subsequently undergo the in situ insertion of sulfur dioxide to generate the crucial alkylsulfonyl radical intermediates. This three-component reaction provides an efficient and facile route for the construction of alkylsulfonylated oxindoles and avoids the use of highly toxic alkylsulfonyl chlorides or alkylsulfonyl hydrazines as alkylsulfonyl sources.

Regioselective synthesis of N-containing polycyclic compounds via radical annulation cyclization of 1,7-dienes with aldehydes.

A convenient method for oxidant-promoted radical cascade acylation or decarbonylative alkylation of 1,7-dienes with aldehydes has been established. This method allows for the rapid construction of N-containing polycyclic skeletons in a highly regio- and stereoselective manner. This transformation provides a simple and efficient method for the preparation of a range of tetrahydro-6H-indeno[2,1-c]quinolinone derivatives by sequential formation of three new carbon-carbon bonds. Additionally, this radical cascade cyclization can selectively convert aldehydes into aroyl/primary aliphatic acyl radicals and secondary or tertiary alkyl radicals.

Visible-light-induced synthesis of 2,4-disubstituted quinolines from o-vinylaryl isocyanides and oxime esters.

A visible-light-induced radical cyclization reaction of o-vinylaryl isocyanides and oxime esters to access various 2,4-disubstituted quinolines was disclosed. Oxime esters were employed as acyl radical precursors via the carbon-carbon bond cleavage. It provided an effective way for the synthesis of 2-acyl-4-arlysubstituted quinolines under mild conditions and exhibited good functional group tolerance and substrate applicability.

Photoredox radical cyclization reaction of o-vinylaryl isocyanides with acyl chlorides to access 2,4-disubstituted quinolines.

We herein report an efficient photoredox radical cyclization reaction of o-vinylaryl isocyanides with acyl chlorides to access a wide range of 2,4-disubstituted quinolines. Preliminary mechanism experiment results suggested that this reaction was initiated by an acyl radical generated from acyl chlorides through a single-electron-transfer (SET) process. This transformation showed good substrate suitability and functional group compatibility at room temperature.

Recent advances in ring-opening of cyclobutanone oximes for capturing SO2, CO or O2via a radical process.

Cyclobutanone oximes and their derivatives are pivotal core structural motifs in organic chemistry. Iminyl-radical-triggered C-C bond cleavage of cyclobutanone oximes delivers an efficient strategy to produce stable distal cyano-substituted alkyl radicals, which can capture SO2, CO or O2 to form cyanoalkylsulfonyl radicals, cyanoalkylcarbonyl radicals or cyanoalkoxyl radicals under mild conditions. In the past several years, cyanoalkylsulfonylation/cyanoalkylcarbonyaltion/cyanoalkoxylation has attracted a lot of interest. In this updated report, the strategies for trapping SO2, CO or O2via iminyl-radical-triggered ring-opening of cyclobutanone oximes are summarized.

Visible-Light-Promoted Decarboxylative Alkylation/Cyclization of Vinylcycloalkanes.

An efficient strategy for visible-light-promoted decarboxylative alkylation of vinylcyclopropanes with alkyl N-(acyloxy)phthalimide esters through the dual C-C bond and single N-O bond cleavage, employing triphenylphosphine and lithium iodide as the photoredox system to synthesize 2-alkylated 3,4-dihydronaphthalenes, has been established. This alkylation/cyclization involves a radical process and undergoes a sequence of N-(acyloxy)phthalimide ester single-electron reduction, N-O bond cleavage, decarboxylative, alkyl radical addition, C-C bond cleavage, and intramolecular cyclization. Moreover, using the photocatalyst Na2-Eosin Y instead of triphenylphosphine and lithium iodide, the vinyl transfer products are acquired when vinylcyclobutanes or vinylcyclopentanes are utilized as alkyl radical receptors.

Visible-light-promoted radical cascade alkylation/cyclization: access to alkylated indolo/benzoimidazo[2,1-a]isoquinolin-6(5H)-ones.

A new protocol is herein described for the direct generation of alkylated indolo/benzoimidazo[2,1-a]isoquinolin-6(5H)-one derivatives by using Hantzsch esters as alkylation radical precursors using a photoredox/K2S2O8 system. This oxidative alkylation of active alkenes involves a radical cascade cyclization process and a sequence of Hantzsch ester single electron oxidation, C-C bond cleavage, alkylation, arylation and oxidative deprotonation.

Cu-catalyzed oxidative denitrogenation of 3-aminoindazoles for the synthesis of isoquinolinones.

A Cu-catalyzed oxidative dual arylation of active alkenes via the cleavage of two C-N bonds of 3-aminoindazoles is presented for constructing isoquinolinones. Importantly, 3-aminoindazoles are used as efficient arylating agents through a radical process. This method has a good substrate scope and functional group compatibility.

Visible-Light-Induced Decarboxylative Alkylation/Ring Opening and Esterification of Vinylcyclopropanes.

A visible-light-induced four-component reaction of vinylcyclopropanes, N-(acyloxy)phthalimide esters, N,N-dimethylformamide (DMF), and H2O through an oxidative ring opening of cyclopropane is presented. This procedure provides a new and effective way to construct formate esters. DMF is employed as both a solvent and the source of CHO. This difunctionalization of vinylcyclopropanes shows good functional group tolerance under room temperature. A radical pathway is involved, and carbonyl oxygen of ester originated from water in this transformation.

Alkylation/Ipso-cyclization of Active Alkynes Leading to 3-Alkylated Aza- and Oxa-spiro[4,5]-trienones.

A method for the preparation of 3-alkylated spiro[4.5]trienones via alkylation/ipso-cyclization of activated alkynes with 4-alkyl-DHPs under transition-metal-free conditions is proposed. This alkylation successively undergoes the generation of alkyl radicals, addition of alkyl radicals to the alkynes, and intramolecular ipso-cyclization. The mechanism studies suggest that the alkylation/ipso-cyclization involves a radical process. This ipso-cyclization procedure shows a series of advantages, such as accessibility, mild conditions, high efficiency, greater safety, and an environmentally friendly method.

Visible-Light-Induced Dual Acylation of Alkenes for the Construction of 3-Substituted Chroman-4-ones.

Heterocyclic compounds, especially oxygen-containing heterocyclic compounds, are crucial moieties in bioactive compounds and drug leads. Substituted chroman-4-ones are a kind of the most significant structural skeletons. Herein, we report a visible-light-induced dual acylation of alkenes for constructing 3-substituted chroman-4-ones, which undergoes a radical tandem cyclization reaction through carbon-carbon bond cleavage of oxime esters by a nitrogen-centered radical strategy. A series of 3-substituted chroman-4-ones were prepared with up to 86% yield.

Transition-metal-free alkylation strategy: facile access to alkylated oxindoles via alkyl transfer.

The transition-metal-free alkylation/cyclization of activated alkenes using Hantzsch ester derivatives as effective alkyl reagents is described. A wide variety of valuable oxindoles was constructed in a single step with excellent selectivity. The reaction occurs through the formation of alkyl radical species followed by the tandem addition/annulation of olefins under oxidative conditions. This protocol is expected to offer inspiration for developing novel and efficient applications of Hantzsch esters in organic synthesis.

The visible-light-induced acylation/cyclization of alkynoates with acyl oximes for the construction of 3-acylcoumarins.

A nitrogen-centered radical-mediated carbon-carbon bond cleavage strategy is described to synthesize functionalized 3-acylcoumarins. The strategy is enabled by the visible-light-induced acylation/cyclization of alkynoates with various acyl oxime compounds in acetonitrile. The difunctionalization of carbon-carbon triple bonds precedes the generation of iminyl radicals, which is followed by the formation of acyl radicals. The acyl radicals then attack the carbon-carbon triple bonds, followed by 5-exo-trig cyclization and 1,2-ester migration. This strategy has wide substrate adaptability and good substituent tolerance.

Visible-Light-Induced Transition-Metal-Free Nitrogen-Centered Radical Strategy for the Synthesis of 2-Acylated 9H-Pyrrolo[1,2-a]indoles.

A convenient and efficient visible-light-induced tandem acylation/cyclization of N-propargylindoles with aryl- or alkyl-substituted acyl oxime esters for the synthesis of 2-acyl-substituted 9H-pyrrolo[1,2-a]indoles under transition-metal-free conditions, which proceeds via nitrogen-centered radical-mediated cleavage of the C-C σ-bond in acyl oxime esters, is established. The aryl or alkyl acyl radicals, which come from acyl oxime esters, attack the C-C triple bonds in N-propargylindoles and then go through intramolecular cyclization/isomerization.

Visible-light-mediated cascade cyanoalkylsulfonylation/cyclization of alkynoates leading to coumarins via SO2 insertion.

A visible-light-mediated tandem cyanoalkylsulfonylation/cyclization of alkynoates with cycloketone oxime compounds for the preparation of 3-cyanoalkylsulfonylcoumarins via SO2 insertion is reported. The difunctionalization of carbon-carbon triple bonds includes a radical mechanism and involves the formation of an iminyl radical, ring-opening of the cycloketone, insertion of SO2, addition of the sulfonyl radical to carbon-carbon triple bonds, ipso-cyclization and ester migration.

Cu-Catalyzed Oxidative Dual Arylation of Active Alkenes: Preparation of Cyanoarylated Oxindoles through Denitrogenation of 3-Aminoindazoles.

A novel and mild Cu-catalyzed oxidative dual arylation of carbon-carbon double bonds in acrylamides with 3-aminoindazoles is proposed for the synthesis of cyanoarylated oxindoles. Notably, 3-aminoindazoles are employed as efficient arylating agents via the cleavage of two C-N bonds. This oxidative dual arylation of active alkenes involves a radical process and undergoes a sequence of 3-aminoindazole oxidation, two-C-N-bond cleavage, cyanoaryl radical addition, and intramolecular cyclization.

Copper-promoted cyanoalkylation/ring-expansion of vinylcyclopropanes with α-C-H bonds in alkylnitriles toward 3,4-dihydronaphthalenes.

A copper-promoted oxidative cyanomethylation/ring-expansion of vinylcyclopropanes with α-C(sp3)-H bonds in alkyl nitriles is established for the generation of 1-cyanoethylated 3,4-dihydronaphthalenes. This cyanomethylation/ring-expansion involves a radical pathway and proceeds via cyanomethyl radical formation, radical addition and ring-expansion. This ring-expansion strategy offers a highly atom-economical route for the construction of nitrile-containing 3,4-dihydronaphthalenes, which can be transformed into other useful products under simple conditions.

Visible-light photoredox-catalyzed dual C-C bond cleavage: synthesis of 2-cyanoalkylsulfonylated 3,4-dihydronaphthalenes through the insertion of sulfur dioxide.

An efficient novel visible-light photoredox-catalyzed dual carbon-carbon bond cleavage of methylenecyclopropanes and cycloketone oximes for the synthesis of 2-cyanoalkylsulfonated 3,4-dihydronaphthalenes through the insertion of sulfur dioxide is established. This dual cleavage of carbon-carbon bonds involves a radical pathway and goes through a sequence of iminyl radical formation, carbon-carbon bond cleavage, sulfur dioxide insertion, sulfonyl radical addition, another carbon-carbon bond cleavage, and intramolecular cyclization.

Visible Light-Catalyzed Cascade Radical Cyclization of N-Propargylindoles with Acyl Chlorides for the Synthesis of 2-Acyl-9H-pyrrolo[1,2-a]indoles.

A novel and convenient visible light-catalyzed tandem radical cyclization of N-propargylindoles with acyl chlorides for accessing 2-acyl-9H-pyrrolo[1,2-a]indoles is established. This transformation involves sequential addition of the acyl radical to the carbon-carbon triple bond, intramolecular cyclization with the 2-position of indole, and isomerization of the carbon-carbon double bond. The experimental results show that this reaction contains a radical pathway and a radical chain process is not the major pathway for the formation of products.

Visible-light promoted one-pot synthesis of sulfonated spiro[4,5]trienones from propiolamides, anilines and sulfur dioxide under transition metal-free conditions.

A novel visible-light promoted sulfonylation/ipso-cyclization of N-arylpropiolamides with arylamines and DABCO·(SO2)2 to synthesize various sulfonated spiro[4,5]trienones is reported. This sulfonylation/ipso-cyclization reaction proceeds via a radical process and undergoes arylsulfonyl radical formation, sulfonylation, and ipso-cyclization. The experimental results indicate that H2O provides an oxygen atom for the construction of the carbonyl group.