Carbonylative cyclization of biaryl enones with aldehydes and oxamic acids.

An oxidative radical-promoted carbonylative cyclization strategy for the synthesis of phenanthren-9-(10H)-one frameworks from biaryl enones using aldehydes as the carbonyl radical sources is disclosed. The reaction proceeds through a sequential addition of a carbonyl radical to the olefin followed by cyclization with an aryl ring. The method is further extended to carbamoyl radicals generated from oxamic acids to access the corresponding phenanthrenones with amide functionalities.

Radical-mediated sulfonylative/thiolative cyclization of biaryl enones to phenanthrone derivatives.

An approach for the assembly of phenanthrone derivatives bearing all carbon quaternary centres has been developed through visible light-promoted tandem sulfonylation/intramolecular-arylation of biaryl enones with sulfonyl chlorides. A series of sulfonylated 10,10-dialkylphenanthrones were obtained in good yields. In addition, the approach has been extended to thiotrifluoromethyl (SCF3) and thiocyanato (SCN) radicals to obtain the corresponding phenanthrones under oxidative conditions. The synthetic utility was also illustrated by the scalability and further transformations of the product.

CAN-Promoted Thiolative ipso-Annulation of Unactivated N-Benzyl Acrylamides: Access to SCN/SCF3/SO2Ar Containing Azaspirocycles.

A variety of acrylamides holding an unactivated N-benzyl group underwent dearomative ipso-cyclization induced by sulfur-centered radicals (SCN/ SCF3/ SO2Ar) in the presence of ceric ammonium nitrate (CAN) as the oxidant to furnish azaspirocycles in good yields. This is the first report on ipso-dearomatization of N-benzyl acrylamides that proceeds without a substituent at the para-position of the aromatic ring. The developed conditions are also found to be suitable for substrates holding substituents such as F, NO2, OMe, OH, and OAc at the para-position. The reaction features water as the source of oxygen, is compatible with a variety of functional groups, and proceeds in a short time.

Access to Diverse Seleno-spirocyclohexadienones via Ag(II)-Catalyzed Selenylative ipso-Annulation with Se and Boronic Acids.

An efficient and straightforward synthesis of diversified seleno-azaspiro-2,5-cyclohexadienones from N-(4-methoxy aryl)propiolamides using elemental selenium and boronic acids has been demonstrated. The reaction proceeds through silver-catalyzed oxidative dearomatization in the presence of potassium persulfate (K2S2O8) as the oxidant. Further, this approach was extended to N-(4-methoxy aryl)propiolates and biaryl ynones to access the corresponding selenylated oxospiro-2,5-cyclohexadienones and spiro[5,5]trienones, respectively. The present three-component method offers the diverse substitutions on selenium involving two C-Se and one C-C bond formations.

Copper(II)-catalyzed oxidative ipso-annulation of N-arylpropiolamides and biaryl ynones with 1,3-diketones: construction of diketoalkyl spiro-trienones.

An unprecedented copper-catalyzed ipso-annulation reaction of N-(p-methoxyaryl)propiolamides with 1,3-diketones has been developed, which enables the assembly of diketoalkylated spiro[4.5]trienones involving oxidative dearomatization in the presence of ammonium persulfate [(NH4)2S2O8] as the oxidant. This protocol was extended to biaryl ynones, efficiently affording the diketoalkylated spiro[5.5]trienones in good yields. The significance of the diketoalkyl functionality has been illustrated by further transformation into 3-pyrazoyl spiro-trienone, a structurally unique motif.

Electrochemical Selenylative Carbannulation of Biaryl Ynones to Seleno-Dibenzocycloheptenones/Spiro[5.5]Trienones.

Electrooxidative-induced synthesis of structurally diverse seleno-dibenzocyclohepten-5-ones and seleno-spiro[5.5]trienones by selenylative carbannulation of biaryl ynones with diaryl diselenide has been developed. The switchable reactivity, intramolecular ortho-annulation or dearomative ipso-annulation, is directed by the substituent present on the ortho-aryl group of aryl-ynone. The prominent features of this method include metal-free, external chemical oxidant-free conditions, and readily accessible substrates.

Expeditious Access to Spiro-Fused 2,5-Cyclohexadienones via Thio(seleno)cyanative ipso-Cyclization.

A facile oxidative dearomatization of N-(p-methoxyaryl)propiolamides has been established for the synthesis of spiro-fused 2,5-cyclohexadienone frameworks via thio(seleno)cyanative ipso-cyclization in the presence of ceric ammonium nitrate (CAN) as the oxidant. The present method, involving the formation of C-S and C-C bonds, was also extended to (p-methoxyaryl)propiolates for thiocyanative ipso-cyclization. Furthermore, the obtained chalcogeno-spirocyclohexadienones were transformed into uniquely functionalized spirocyclohexadienone derivatives.

Ag-Catalyzed Oxidative ipso-Cyclization via Decarboxylative Acylation/Alkylation: Access to 3-Acyl/Alkyl-spiro[4.5]trienones.

A strategy to functionalized spiro[4.5]trienones, by domino silver-catalyzed decarboxylative acylation or alkylation/ ipso-cyclization of N-arylpropiolamides with α-keto acids/alkyl carboxylic acids, is presented. This transformation offers a wide range of substituted 3-acyl/alkyl-spiro[4.5]trienones in high yields with a broad substrate scope. The approach was further extended to access fused tricyclic frameworks, 6,7-dihydro-3H-pyrrolo[2,1-j]quinoline-3,9(5H)-diones.

One-Pot Assembly of 3-Hydroxycarbazoles via Uninterrupted Propargylation/Hydroxylative Benzannulation Reactions.

A novel strategy for the synthesis of 3-hydroxycarbazoles involving the consecutive propargylation/palladium-catalyzed hydroxylative benzannulation of indole-2-carbonyls with propargylic alcohols has been exploited. This one-pot procedure leads to a wide range of substituted 3-hydroxycarbazoles in high yield with a broad substrate scope. The method was further extended to access furano-carbazole derivatives from dialkynols via tandem annulations.