Synthesis of Acylation Polycyclic Derivatives via Regioselective Acylation/Cyclization of 1,7-Dienes with Acyl Oxime Esters.

A visible-light-induced radical cascade regioselective acylation/cyclization of 1,7-dienes with acyl oxime esters for the preparation of acylation polycyclic compounds via NCR-mediated C-C σ-bond cleavage is established. The transformation involves the cleavage of the C-C σ-bond in acyl oxime esters and selective addition of the electron neutral C═C bonds in 1,7-dienes for the synthesis of acyl polycyclic quinolinone derivatives, not the traditional seven-membered ring products. The strategy offers several advantages, including broad substrate tolerance, no need for bases, hyperstoichiometric radical initiators, and other auxiliaries.

Photoredox Ring Opening 1,2-Alkylarylation of Alkenes with Sulfonium Salts Toward Thioether-Substituted Oxindoles.

A novel strategy for the difunctionalization of electron-deficient alkenes with aryl sulfonium salts to access remote sulfur-containing oxindole derivatives by using in situ-formed copper(I)-based complexes as a photoredox catalyst is presented. This method enables the generation of the C(sp3)-centered radicals through site selective cleavage of the C-S bond of aryl sulfonium salts under mild conditions. Moreover, the oxidation reactions of desired products provide a new strategy for the preparation of sulfoxide or sulfone-containing compounds. Importantly, this approach can be easily applied to late-stage modification of pharmaceuticals molecules.

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.

Zn-Catalyzed Dehydroxylative Phosphorylation of Allylic Alcohols with P(III)-Nucleophiles.

A novel and efficient protocol for the synthesis of diarylallyl-functionalized phosphonates, phosphinates, and phosphine oxides through the zinc-catalyzed dehydroxylative phosphorylation of allylic alcohols with P(III)-nucleophiles via a Michaelis-Arbuzov-type rearrangement is reported. A broad range of allylic alcohols and P(III)-nucleophiles (P(OR)3, ArP(OR)2, and Ar2P(OR)) are well tolerated in this reaction, and the expected dehydroxylative phosphorylation products could be synthesized with good to excellent yields under the optimal reaction conditions. The reaction can be easily scaled up at a gram-synthesis level. Furthermore, through the step-by-step control experiments, kinetic study experiments, and 31P NMR tracking experiments, we acquired insights into the reaction and proposed the possible mechanism for this transformation.

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.

Electro-oxidative three-component cascade coupling of isocyanides with elemental sulfur and amines for the synthesis of 2-aminobenzothiazoles.

2-Aminobenzothiazoles are commonly encountered in various functional compounds. Herein, we disclose an electro-oxidative three-component reaction for the effective synthesis of 2-aminobenzothiazoles under mild conditions, utilizing non-toxic and abundant elemental sulfur as the sulfur source. Both aliphatic amines and aryl amines demonstrate good compatibility at room temperature, highlighting the broad functional group tolerance of this approach. Additionally, elemental selenium demonstrated reactivities comparable to those of elemental sulfur.

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-Induced Synthesis of Alkylsulfonated Isoquinolinones from 2-Aryl Indoles/Benzimidazoles through Insertion of Sulfur Dioxide.

A visible-light-induced three-component reaction of 2-aryl indoles/benzimidazoles, Hantzsch esters, and sodium pyrosulfite through a radical cascade cyclization process with the insertion of sulfur dioxide is described. It provides a novel and powerful way for the synthesis of alkylsulfonated isoquinolinones. Hantzsch esters and Na2S2O5 are employed as alkyl radical precursors and SO2 surrogate, respectively. This transformation exhibits good functional group tolerance and substrate applicability under mild conditions.

Ruthenium-Catalyzed 1,6-Hydroalkylation of para-Quinone Methides with Ketones via the in Situ Activation of C(sp3)-H Bonds.

A simple and efficient method for the ruthenium-catalyzed 1,6-hydroalkylation of para-quinone methides (p-QMs) with ketones via the in situ activation of C(sp3)-H bonds has been disclosed. Without the need for preactivation of the substrates and oxidant, a broad range of p-QMs and ketones are well tolerated, producing the expected 1,6-hydroalkylation products with moderate to good yields. Step-by-step control experiments and DFT calculation were conducted systematically to gain insights for the plausible reaction mechanism. This finding may have potential application in the selective diarylmethylation of ketones at the α-C position in organic synthesis.

Copper-Catalyzed Aerobic Oxidative/Decarboxylative Phosphorylation of Aryl Acrylic Acids with P(III)-Nucleophiles.

A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles via the Michaelis-Arbuzov rearrangement for the synthesis of ß-ketophosphine oxides, ß-ketophosphinates, and ß-ketophosphonates is reported. The present reaction could be conducted effectively without the use of a ligand and a base. Various kinds of aryl acrylic acids and P(III)-nucleophiles are tolerated in the transformation, generating the desired ß-keto-organophosphorus compounds as a valuable class of phosphorus-containing intermediates with good to excellent yields. In addition, the possible mechanism and kinetic studies for the reaction have been explored by step-by-step control experiments and competitive experiments, and the results proved that this transformation may follow second-order chemical kinetics as well as involve a radical process.

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.

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.

Metal-Free, Acid/Phosphine-Induced Regioselective Thiolation of p-Quinone Methides with Sodium Aryl/Alkyl Sulfinates.

A simple and efficient method for the regioselective thiolation of p-quinone methides with sodium aryl/alkyl sulfinates has been established using an acid/phosphine-induced radical route under transition-metal-free conditions. A broad range of sodium aryl/alkyl sulfinates and p-quinone methides (p-QMs) are compatible for the reaction, giving the expected products with good to excellent yields. Control experiments were also performed to gain insights into the generation mechanism of thiyl radicals and hydrogen-atom transfer process. This protocol provides a safe and feasible way for the formation of carbon-sulfur bonds.

Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles.

A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.

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.

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.

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.