Synthesis of Chalcogenylchromenes through Cyclization of Propargylic Aryl Ethers.

We describe here for the first time the synthesis of 2-(chalcogenyl)-3H-benzo[f]chromenes and the new 3-(phenylselanyl)-2H-chromenes by the radical or electrophilic cyclization of propargylic aryl ethers in the presence of diorganyl diselenides or ditellurides using Oxone as a green oxidant and acetonitrile as solvent in a sealed tube at 100 °C. In this study, thirty-one chalcogenylchromenes with a broad substrate scope were prepared in moderate to excellent yields (50-98%), including compounds derived from natural products.

Synthesis of benzo[b]chalcogenophenes fused to selenophenes via intramolecular electrophilic cyclization of 1,3-diynes.

We describe herein an alternative and transition-metal-free procedure for the access of benzo[b]chalcogenophenes fused to selenophenes via intramolecular cyclization of 1,3-diynes. This efficient protocol involves a double cyclization of 1,3-diynyl chalcogen derivatives promoted by the electrophilic species of organoselenium generated in situ by the oxidative cleavage of the Se-Se bond of dibutyl diselenide using Oxone® in acetonitrile as solvent in an open-flask at 80 °C. In this study, 15 selenophenes with broad substrate scope were prepared in moderate to excellent yields (55-98%) with short reaction times (0.5-3.0 h).

Synthesis of 3,4-Bis(Butylselanyl)Selenophenes and 4-Alkoxyselenophenes Promoted by Oxone®.

We describe herein an alternative transition-metal-free procedure to access 3,4-bis(butylselanyl)selenophenes and the so far unprecedented 3-(butylselanyl)-4-alkoxyselenophenes. The protocol involves the 5-endo-dig electrophilic cyclization of 1,3-diynes promoted by electrophilic organoselenium species, generated in situ through the oxidative cleavage of the Se-Se bond of dibutyl diselenide using Oxone® as a green oxidant. The selective formation of the title products was achieved by controlling the solvent identity and the amount of dibutyl diselenide. By using 4.0 equiv of dibutyl diselenide and acetonitrile as solvent at 80 °C, four examples of 3,4-bis(butylselanyl)selenophenes were obtained in moderate to good yields (40-78%). When 3.0 equiv of dibutyl diselenide were used, in the presence of aliphatic alcohols as solvent/nucleophiles under reflux, 10 3-(butylselanyl)-4-alkoxyselenophenes were selectively obtained in low to good yields (15-80%).

Recent Advances in the Synthesis of Selenophenes and Their Derivatives.

The selenophene derivatives are an important class of selenium-based heterocyclics. These compounds play an important role in prospecting new drugs, as well as in the development of new light-emitting materials. During the last years, several methods have been emerging to access the selenophene scaffold, employing a diversity of cyclization-based synthetic strategies, involving specific reaction partners and particularities. This review presents a comprehensive discussion on the recent advances in the synthesis of selenophene-based compounds, starting from different precursors, highlighting the main differences, the advantages, and limitations among them.

Telescoping Synthesis of 4-Organyl-5-(organylselanyl)thiazol-2-amines Promoted by Ultrasound.

In this work, we describe the synthesis of new 4-organyl-5-(organylselanyl)thiazol-2-amine hybrids through a one-pot two-step protocol. The transition metal-free method involves the use of ultrasound as an alternative energy source and Oxone® as oxidant. To obtain the products, a telescoping approach was used, in which 4-organylthiazol-2-amines were firstly prepared under ultrasonic irradiation, followed by the addition of diorganyl diselenides and Oxone®. Thus, 16 compounds were prepared, with yields ranging from 61 % to 98 %, using 2-bromoacetophenone derivatives and diorganyl diselenides as easily available starting materials.

Synthesis of 5-Selenosubstituted Spirocyclopenta[b]pyridine-2,5-dien-4-ones and Benzo[h]quinolines via Radical Cyclization of Arylethynylpyridines.

A practical strategy for obtaining novel 5-seleno-substituted spirocyclopenta[b]pyridines-2,5-dien-4-ones and benzo[h]quinolines via radical cyclization is reported. The synthetic protocol explores the reaction between arylethynylpyridines and diorganyl diselenides in acetonitrile as solvent and Oxone® as oxidant at 82 °C. This easy-to-handle, eco-friendly metal-free approach was carried out under an open atmosphere, affording functionalized organoselenium compounds in good to excellent yields. Control experiments and scale-up test were performed to demonstrate the efficiency of this methodology.