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.

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.

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.

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.

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.

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.