A transition-metal-free electrochemical chalcogenative cyclization of 2-alkynyl aryl oxime with dichalcogenides has been established to assemble valuable 4-organochalcogen isoquinolines concisely. This protocol proceeds via constant electrolysis in a user-friendly undivided cell setup. It circumvents the necessity of transition metal catalysts, chemical oxidants, and harsh reaction conditions. The practical utilities of the current protocol were illustrated by excellent functional group tolerance, remarkable regio-selectivity, easy scalability, mild reaction conditions, and transformable 4-organochalcogen isoquinoline products.
A novel mechanoredox-enabled synthesis of aromatic and aliphatic isothiocyanates from primary amines and carbon disulfide under ball milling conditions using a piezoelectric material (BaTiO3) as the redox catalyst has been developed. This method displays several features, such as short reaction time, operational simplicity, room temperature and air conditions, minimal solvent, broad substrate scope, and recyclable cheap catalyst. Preliminary mechanistic studies revealed that highly polarized piezoelectric material acted as a single-electron transfer (SET) oxidation reagent for the key desulfurization process.
Controlling the reaction selectivity to achieve a precision synthesis is a constant concern for chemists. Here, we report a palladium-catalyzed deaminative coupling of propargylamines with arylboronic acids to generate allene skeletons. Importantly, this approach allows the regioselective γ-arylation of unactivated propargyl tertiary amines to access various allenes in the absence of amino-activating reagents. We present a wide range of propargylamines and boronic acids and demonstrate the synthetic application of the target products to construct valuable compounds.
The selective synthesis of polysubstituted quinoline has been recognized as an important but highly challenging transformation. In this study, a highly efficient method for the synthesis of 2,4-bisthioquinolines has been developed through a copper(II)-promoted tandem cycloaddition of o-alkynylphenyl isothiocyanates, utilizing inexpensive and readily available sodium sulfide (Na2S) as the sulfur source. This transformation enables the direct synthesis of 2,4-bis(thioquinoline) heterocycles via the formation of C–C and C–S bonds in a one-pot reaction, demonstrating excellent tolerance for various functional groups.
Herein, we report an aerobic oxidative cross-dehydrogenative coupling (CDC) reaction between thiols and phosphonothioates. The reactions were conducted under mild and transition-metal-free conditions in the presence of air. Not only aryl thiols but also alkyl thiols were successfully coupled with phosphonothioates to form the corresponding phosphorodithioates in good to excellent yields.