Radical relay cyclization/C-C bond formation of allyloxy-tethered aryl iodides with quinoxalin-2(1H)-ones via polysulfide anion photocatalysis.

A visible-light-induced radical relay cyclization/C-C bond formation of quinoxalin-2(1H)-ones with allyloxy-tethered aryl iodides using polysulfide anions as a photocatalyst is described. This protocol allows efficient access to a variety of complicated molecules bearing both quinoxalin-2(1H)-one and 2,3-dihydrobenzofuran motifs in high yields under mild reaction conditions with a broad range of substrates.

Metal-Free Synthesis of 2H-Indazole Skeletons by Photochemistry or Thermochemistry.

A simple and tuned synthesis of a 2H-indazole skeleton under metal-free conditions was developed. Under visible-light irradiation at room temperature, 2-((aryl/alkyl/H)ethynyl))aryltriazenes reacted with arylsulfinic acids to afford 3-functionalized 2H-indazoles without extra photocatalyst via an electron donor-acceptor complex. In the presence of arylsulfinic acid, 2-(ethynyl)aryltriazenes underwent an intramolecular oxidation/cyclization to provide 2H-indazole-3-carbaldehydes at 50 °C in air.

Photoinduced Radical Cyclization of 2-Alkynylthioanisoles with Disulfides without an External Photocatalyst.

An efficient strategy for the synthesis of 3-arylthiobenzo[b]thiophenes via a photodriven radical cyclization of 2-alkynylthioanisoles with disulfide was developed. The reaction proceeded smoothly under visible-light irradiation without any external photocatalyst and generated the desired products in high yields with good functional group tolerance.

Electrophilic Halospirocyclization of N-Benzylacrylamides to Access 4-Halomethyl-2-azaspiro[4.5]decanes.

An electrophilic spirocyclization of N-benzylacrylamides with N-halosuccinimides (NXS) as the halogenating reagents has been developed. This reaction is carried out at room temperature under simple conditions without relying on metal reagents, photochemistry, or electrochemistry, providing a fast and efficient route to synthesize a wide variety of 4-halomethyl-2-azaspiro[4.5]decanes with satisfactory yields. The approach is further highlighted through gram-scale synthesis and diverse transformations of the spiro products.

Electrochemical monofluoroalkylation cyclization of N-arylacrylamides to construct monofluorinated 2-oxindoles.

An electrochemical monofluoroalkylation cyclization of N-arylacrylamides to synthesize monofluorinated 2-oxindoles has been developed, which employs common dimethyl 2-fluoromalonate as a monofluoroalkyl radical precursor and obviates the use of prefunctionalized monofluoroalkylation reagents and sacrificial oxidants. A variety of monofluorinated nitrogen-containing heterocyclic compounds were efficiently obtained with satisfactory yields from readily available materials.

Microwave-promoted radical addition/cyclization of biaryl vinyl ketones with diacyl peroxides in water under metal-free conditions.

This communication reports an efficient microwave-promoted radical addition/cyclization reaction of biaryl vinyl ketones with diacyl peroxides in water under metal-free conditions. A series of 10-methyl-10-benzyl(alkyl)phenanthren-9(10H)-ones were obtained in high yields with good functional group tolerance.

Visible-light-induced halocyclization of 2-alkynylthioanisoles with simple alkyl halides towards 3-halobenzo[b]thiophenes without an external photocatalyst.

A new strategy for the preparation of 3-halobenzo[b]thiophenes via a photo-driven halocyclization/demethylation of 2-alkynylthioanisoles with simple alkyl halides was developed. The reaction can proceed smoothly at room temperature under visible-light irradiation without any external photocatalyst, and the protocol has a range of advantages, including simplicity and mildness of the reaction conditions, good functional-group tolerance, and excellent yields of the products.

Electrochemical Dearomatizing Spirocyclization of Alkynes with Dimethyl 2-Benzylmalonates to Spiro[4.5]deca-trienones.

An electrochemical dearomatizing spirocyclization of alkynes with dimethyl 2-benzylmalonates for the preparation of spiro[4.5]deca-trienones has been developed. This approach adopts ferrocene (Cp2Fe) as an electrocatalyst to produce carbon-centered radical intermediates from C-H-based malonates, which obviates the forthputting of noble-metal reagents, sacrificial chemical oxidants and 2-bromomalonates. A wide variety of spiro compounds are efficiently prepared with satisfactory results under mild conditions.

Synthesis of Fully Substituted 5-(o-Hydroxybenzoyl)imidazoles via Iodine-Promoted Domino Reaction of Aurones with Amidines.

An iodine-promoted domino reaction of aurones with amidines has been successfully explored. The reaction proceeds in a consecutive manner containing Michael addition, iodination, cyclization from intramolecular nucleophilic substitution, and dehydrogenative aromatization from spiro ring opening. Following this novel strategy, a variety of 1,2,4-trisubstituted 5-(o-hydroxybenzoyl)imidazoles were efficiently synthesized in moderate to good yields from readily available starting materials. A plausible mechanism has been proposed.

Electrochemical Regioselective Cross-Dehydrogenative Coupling of Indoles with Xanthenes.

An electrochemical cross-dehydrogenative coupling of indoles with xanthenes has been established at room temperature. This coupling reaction could proceed in the absence of any catalyst or external oxidant, and generate the indole derivatives in moderate yields. Mechanistic experiments support that a radical pathway maybe involved in this reaction system.

Microwave-accelerated and benzoyl peroxide (BPO)-initiated cyclization of 1,5-enynes having cyano groups with cyclic alkanes under metal-free conditions.

A novel and efficient method for preparing exocyclic indan derivatives, with this method involving benzoyl peroxide (BPO)-initiated cyclization of 1,5-enynes having cyano groups with simple cyclic alkanes under microwave irradiation, has been developed. The presented approach showed advantages of simple conditions, an environmentally friendly protocol, good functional-group tolerance, and high yields of products.

Synthesis of polychloromethylated and halogenated spiro[5,5]trienones via dearomative spirocyclization of biaryl ynones.

We disclosed a selective polychloromethylation and halogenation reaction of alkynes via a radical addition/spirocyclization cascade sequence, in which polyhaloalkanes were used as the precursor for polyhalomethyl and halogen radicals. Using this strategy, a series of valuable halogen-, CHCl2- or CCl3-containing spiro[5,5]trienones were synthesized in good yields with good functional group tolerance in one pot under simple and mild conditions. It is noted that an unprecedented halogenation instead of dibromomethylation was achieved when CH2Br2 was used in this work.

Merging cobalt and photoredox catalysis for the C8-H alkoxylation of 1-naphthylamine derivatives with alcohols.

A combined cobalt and photoredox catalysis system to realize the C8-H alkoxylation of 1-naphthylamine derivatives with alcohols was developed. Using commercially available alkyl alcohols as raw materials and Co(OAc)2 and rose bengal as catalysts, 1-naphthylamine derivatives reacted with alcohols to generate the corresponding C8-H alkoxylation products in good yields.

Facile synthesis of carbamoylated benzimidazo[2,1-a]isoquinolin-6(5H)-ones via radical cascade cyclization under metal-free conditions.

A highly efficient synthesis of carbamoylated benzimidazo[2,1-a]isoquinolin-6(5H)-ones using 2-arylbenzoimidazoles and oxamic acids was developed. This strategy tolerated various substrates as the starting materials to generate the corresponding products in good yields under metal-free conditions.

Visible-Light-Induced Decarboxylative Cyclization/Hydrogenation Cascade Reaction to Access Phenanthridin-6-yl(aryl)methanol by an Electron Donor-Acceptor Complex.

A novel and efficient visible-light-induced decarboxylative cyclization/hydrogenation cascade reaction of α-oxocarboxylic acids and 2-isocyanobiaryls has been developed. Without the need of any external photosensitizer, oxidant, and reductant, this method offers a mild and green approach for the synthesis of diverse alcohols in moderate to good yields. A mechanism indicated that an electron donor-acceptor complex-driven decarboxylation, radical addition/cyclization, and in situ photochemical reduction of ketones to alcohols could be involved in the reaction.

Aqueous ZnCl2 Complex Catalyzed Prins Reaction of Silyl Glyoxylates: Access to Functionalized Tertiary α-Silyl Alcohols.

An efficient Prins reaction of silyl glyoxylates in the presence of an aqueous ZnCl2 complex as a catalyst was developed, providing functionalized tertiary α-silyl alcohols in high yields under mild conditions. A preliminary investigation indicated that the aqueous ZnCl2 complex acted as a dual functional catalyst of Brønsted and Lewis acid to activate the carbonyl groups of silyl glyoxylates via a dual-activation model.

BF3·OEt2-mediated cyclization of ß,γ-unsaturated oximes and hydrazones with N-(arylthio/arylseleno)succinimides: an efficient approach to synthesize isoxazoles or dihydropyrazoles.

A highly efficient BF3·OEt2-mediated cyclization of ß,γ-unsaturated oximes and tosylhydrazones with N-(arylthio/arylseleno)succinimides has been established for the construction of N-heterocycles in a one-step manner. This metal-free cyclization provides direct access to isoxazoles and dihydropyrazoles in good to excellent yields at room temperature. The mechanistic experiments support the formation of a cationic species PhS+ which plays a critical role in this cyclization process.

Room temperature iron(ii)-catalyzed radical cyclization of unsaturated oximes with hypervalent iodine reagents.

Here, we disclose an iron(ii)-catalyzed I-O bond cleavage of Koser's hypervalent iodine reagents (HIRs) that initiated the radical cyclization of unsaturated oximes at room temperature. This strategy is successfully applied for the construction of the isoxazoline backbone in an efficient manner. In particular, the direct introduction of a TsO group into products facilitates their late-stage transformations in organic synthesis.

"On Water" Direct Catalytic Vinylogous Aldol Reaction of Silyl Glyoxylates.

The unique reactivity of water in the direct catalytic vinylogous aldol reaction of silyl glyoxylates is reported. With the hydrogen-bonding networks from water, the unfavorable homogeneous reactions in organic solvents were severely suppressed, and the "on water" relay chemistry for the vinylogous aldol reaction was realized in heterogeneous conditions (water as solvent), providing the desired α-hydroxysilanes with a quaternary carbon center in high yields. Moreover, new insights on the role of water in biological systems were demonstrated.

Annulation of Benzamides with Arynes Using Palladium with Photoredox Dual Catalysis.

Efficient annulation of benzamides with arynes using palladium and photoredox dual catalysis under an oxygen atmosphere is disclosed, which circumvents the use of external toxic metal oxidant and proceeds readily via aryne insertion at room temperature to construct the phenanthridinone backbone.