Synthesis of isothiocyanato alkyl sulfides from alkenes using KSCN and DMTSM.

A method for the synthesis of isothiocyanato alkyl sulfides from KSCN and DMTSM under metal-free conditions has been developed. The features of this reaction are low-cost, readily accessible starting materials and the use of KSCN as nucleophiles for C-NCS bond formation. Alkenes with various substituted groups react smoothly and the desired products are obtained in moderate to good yields.

TFA-Mediated Synthesis of 1,2,4-Oxadiazoles from Carbamates and Nitriles.

An unprecedented protocol for the synthesis of 1,2,4-oxadiazoles from carbamates has been developed by employing nitriles as both substrates and solvents. This one-pot procedure achieves the formation of C═N bonds via TFA-mediated [3+2] annulation. A series of 1,2,4-oxadiazoles are synthesized in moderate to good yields.

I2-catalyzed synthesis of 3-aminopyrrole with homopropargylic amines and nitrosoarenes.

The synthesis of 3-aminopyrrole using the amination reagent nitrosoarenes and homopropargylic amines catalyzed by I2 through cyclization and amination has been developed. This protocol features excellent functional group tolerance and mild reaction conditions, yielding 3-aminopyrroles in moderate to good yields without a metal catalyst. This method realizes the construction and amination of the 3-aminopyrroles in which nitrosoarenes serve as the amine source and oxidant.

I2-Mediated [6 + 1] Annulation of Alkynes with MsONH3OTf: Direct Synthesis of Benzo[b]azepines.

The synthesis of benzo[b]azepines using protonated aminating reagent (MsONH3OTf) and alkynes through I2-mediated [6 + 1] annulation reaction has been developed. This protocol features excellent functional group tolerance and mild reaction conditions and affords the benzo[b]azepines in moderate to good yields under metal-free reaction conditions.

Metal-Free C-S Bond Formation in Elemental Sulfur and Cyclobutanol Derivatives: The Synthesis of Substituted Thiophenes.

A general approach for the metal-free synthesis of thiophenes by tert-cyclobutanols and elemental sulfur has been developed. This protocol provides a strategy for constructing multisubstituted thiophene derivatives via C-S bond formation under air. This reaction shows good functionality tolerance under the reaction conditions, and the mechanism is validated by control experiments and density functional theory calculations.

Synthesis of Benzimidazo[2,1-a]isoquinoline and Indolo[2,1-a]isoquinoline Derivatives via Copper-Catalyzed Silylation/Methylation of 2-Arylindoles and 2-Arylbenzimidazoles.

A one-pot method for the synthesis of silylsubstituted/methylsubstituted indolo[2,1-a]isoquinolin-6(5H)-ones and benzimidazo[2,1-a]isoquinoline-6(5H)-ones via copper(II)-initiated silylation/methylation of 2-arylindoles and 2-arylbenzimidazoles was developed. In this procedure, the C-Si bond and C-C bond were constructed by radical addition and cyclization. A series of 2-arylindole and 2-arylbenzimidazole derivatives were facilely transformed to indolo[2,1-a]isoquinolines and benzimidazo[2,1-a]isoquinolines in 39-83% yields.

Iron-Catalyzed Ring Expansion of Cyclobutanols for the Synthesis of 1-Pyrrolines by Using MsONH3OTf.

The synthesis of 1-pyrrolines from cyclobutanol derivatives and an aminating reagent (MsONH3OTf) has been developed. This one-pot procedure achieves C-N bond/C═N bond formation via ring expansion. A series of 1-pyrroline derivatives are synthesized in moderate to good yields under mild conditions.

I2 -Promoted Intramolecular Oxidative Cyclization of Butenyl Anilines: A Facile Route to Benzo[b]azepines.

A metal-free approach for the synthesis of seven-membered N-heterocycles has been developed by the I2 -promoted intramolecular cross-coupling/annulation of butenyl anilines. This cyclization reaction involves C-H activation and C-C bond formation and exhibits good functional group tolerance. A series of benzo[b]azepine derivatives are obtained in moderate to good yields.

A catalyst-free method for the synthesis of 1,4,2-dithiazoles from isothiocyanates and hydroxylamine triflic acid salts.

A catalyst-free method for the preparation of 1,4,2-dithiazoles is developed by reactions of isothiocyanates with hydroxylamine triflic acid salts. This reaction achieves C-S, C-N, and S-N bond formation, and a range of products are obtained in moderate to good yields. The obvious feature is using shelf-stable hydroxylamine triflic acid salts as a N source to synthesize heterocycles under mild conditions.

Synthesis of 3-benzylidenetetrahydrofurans: Tf2O-catalyzed hydroxylation/cyclization of cyclopropanemethanols with DMSO.

A formal hydroxylation/cyclization of cyclopropanemethanols with DMSO is described, which involves isomerization and cyclization under Tf2O catalysis. This reaction undergoes ring-opening of the cyclopropane moiety to generate homoallylic alcohols, which react with DMSO to produce 3-benzylidenetetrahydrofurans. With various substituted groups on cyclopropanemethanols the reactions proceed smoothly and the desired 3-benzylidenetetrahydrofurans are obtained in moderate to good yields.

B(C6F5)3-Catalyzed cyclization of alkynes: direct synthesis of 3-silyl heterocyclic compounds.

An efficient one-pot strategy for easy access to 3-silyl heterocyclic compounds was developed via a B(C6F5)3-catalyzed cycloaddition reaction of o-(1-alkynyl)(thio)anisoles or o-(1-alkynyl)-N-methylaniline. In this reaction, benzenethiophene, benzofuran or indole skeletons could be constructed by an intermolecular cyclization with diphenylsilane. This protocol elicited moderate-to-good yields with metal-free reaction systems.

TFA-Catalyzed [3+2] Spiroannulation of Cyclobutanols: A Route to Spiro[cyclobuta[a]indene-7,1'-cyclobutane] Skeletons.

A straightforward method for the synthesis of spiro[cyclobuta[a]indene-7,1'-cyclobutane] derivatives from cyclobutanols has been developed via one-pot [3+2] spiroannulation. A series of new spiro[cyclobuta[a]indene-7,1'-cyclobutane] derivatives are facilely synthesized in good yields under mild reaction conditions.

TFAA-Catalyzed Annulation Synthesis of Spiro Pyrrolo[1,2-a]quinoxaline Derivatives from 1-(2-Aminophenyl)pyrroles and Benzoquinones/Ketones.

A metal-free trifluorosulfonate anhydride (TFAA)-catalyzed strategy for the synthesis of spiro pyrrolo[1,2-a]quinoxalines from 1-(2-aminophenyl)pyrroles and benzoquinones/ketones has been developed. With this general method, spiro pyrrolo[1,2-a]quinoxalines have been accessed via nucleophilic addition and cyclization. This reaction exhibits good functional group tolerance, and a wide range of products are obtained in moderate to good yields.

A convenient access to allylic triflones with allenes and triflyl chloride in the presence of (EtO)2P(O)H.

A simple method for the preparation of allylic triflones from allenes and triflyl chloride in the presence of (EtO)2P(O)H has been developed. The features of this reaction are catalyst-free and simple starting substrates. This method tolerates diverse functional groups and substituted allylic triflones are obtained in moderate to good yields.

Copper-catalyzed tandem aerobic oxidative cyclization for the synthesis of 4-cyanoalkylpyrrolo[1,2-a]quinoxalines from 1-(2-aminophenyl)pyrroles and cyclobutanone oxime esters.

A copper-catalyzed tandem ring-opening/cyclization reaction for the synthesis of 4-cyanoalkylpyrrolo[1,2-a]quinoxalines from 1-(2-aminophenyl)pyrroles and cyclobutanone oxime esters has been developed. This reaction involves C-C bond cleavage and C-C and C-N bond constructions with good functional group tolerance. A wide range of products are obtained in moderate to good yields under mild conditions.

Cu-Catalyzed Tandem Aerobic Oxidative Cyclization for the Synthesis of 3,3'-Bipyrroles from the Homopropargylic Amines.

A Cu-catalyzed method for the synthesis of 3,3'-bipyrroles from homopropargylic amines through tandem aerobic oxidative cyclization involving the formation of C-C bond has been developed. The features of this reaction are a small number of Cu catalysis and simple starting substrates. Moreover, this procedure exhibits good functional group tolerance and a series of 3,3'-bipyrroles derivatives are obtained in moderate to good yields.

Fe-Catalyzed tandem cyclization for the synthesis of 3-nitrofurans from homopropargylic alcohols and Al(NO3)3·9H2O.

Al(NO3)3·9H2O as a nitro source for the synthesis of 3-nitrofurans from homopropargylic alcohols through Fe-catalyzed tandem cyclization is described. In this transformation, the substituted nitrofurans are obtained through nitration and cyclization. The substrate homopropargylic alcohols with different groups participate smoothly in this process and the desired substituted nitrofurans were obtained in moderate yields.

tert-Butyl Nitrite Promoted Oxidative Intermolecular Sulfonamination of Alkynes to Synthesize Substituted Sulfonyl Pyrroles from the Alkynylamines and Sulfinic Acids.

tert-Butyl nitrite promoted oxidative intermolecular sulfonamination of alkynes to synthesize substituted sulfonyl pyrroles from the alkynylamines and sulfinic acids via tandem addition/cyclization was developed. This reaction is performed well by employing tert-butyl nitrite as the oxidant, and various substituted sulfonyl pyrroles are formed in moderate to good yields with no requirement of metal catalysis.

Cleavage of C-C Bonds for the Synthesis of C2-Substituted Quinolines and Indoles by Catalyst-Controlled Tandem Annulation of 2-Vinylanilines and Alkynoates.

The strategy for the synthesis of C2-substituted indoles and quinolines from 2-vinylanilines and alkynoates through C-C bond cleavage is developed. With these general methods, 2-substituted indoles and quinolines can be accessed via tandem Michael addition and cyclization with no requirement of oxidant. This strategy not only provides a method for the synthesis C2-substituted indoles in good yields through the simultaneous cleavage of C═C and C≡C bonds under metal-free conditions but also provides a simple method for the generation of the C2-substituted quinolines in moderate yields via Pd-catalyzed C≡C bond cleavage.

FeCl3-Catalyzed synthesis of pyrrolo[1,2-a]quinoxaline derivatives from 1-(2-aminophenyl)pyrroles through annulation and cleavage of cyclic ethers.

A straightforward Fe-catalyzed method for the synthesis of pyrrolo[1,2-a]quinoxalines from 1-(2-aminophenyl)pyrroles and cyclic ethers, which includes functionalization of C(sp3)-H bonds and the construction of C-C and C-N bonds, has been developed. The features of this reaction are Fe catalysis, low-cost and readily accessible starting materials. Moreover, this procedure exhibits good functional group tolerance and a series of pyrrolo[1,2-a]quinoxaline derivatives are obtained in moderate to good yields.