Copper-Catalyzed Tandem Cyclization/Chalcogenation with Elemental S8/Se: Concise Synthesis of 3-(ß-Hydroxychalcogen)benzofurans.

A novel copper-catalyzed cyclization/chalcogenation of o-alkynylphenols with epoxides and elemental S8/Se was developed for the synthesis of a 3-chalcogen-benzofuran architecture in a domino process with no intermediate isolation or purification. Various sensitive functional groups were compatible at room temperature and furnished chalcogenation derivatives in moderate to good yields.

Synthesis of Isoxazoles via One-Pot Oxidation/Cyclization Sequence from Propargylamines.

A facile strategy for the synthesis of isoxazoles has been efficaciously developed, which involves oxidation of propargylamines to the corresponding oximes followed by CuCl-mediated intramolecular cyclization of the latter. This protocol shows a straightforward way to construct a series of isoxazole cores with a wide range of functional group compatibility. Meanwhile, a gram-scale experiment and synthetic applications can be successfully operated.

Access to Sulfur-Containing Bisheterocycles through Base-Promoted Consecutive Tandem Cyclization/Sulfenylation with Elemental Sulfur.

A convenient and efficient tandem cyclization/sulfenylation of o-alkynyl-phenols/-anilines/enaminones for the synthesis of diverse sulfur-containing bisheterocycles has been developed using stable, odorless, and easy-to-handle elemental S8 as a building block under green chemistry conditions. Notably, a one-step simple base-mediated organic transformation affords a benzofuran (indole or chromone) ring and two C-S bonds. Attractive features of this methodology include the absence of a metal catalyst, mild conditions, good functional group tolerance, and valuable product structures.

Selective oxidative ß-C-H bond sulfenylation of tetrahydroisoquinolines with elemental sulfur.

In this article, a convenient and efficient KIO3-promoted oxidative sulfenylation at the ß-position of tetrahydroisoquinolines and subsequent aromatization in the presence of elemental S8 is presented. The reaction proceeds with moderate to good yields via a double C-S formation process. A wide range of structurally diverse 4-sulfenylisoquinolines/3-sulfenylpiperidine were synthesized with excellent functional group tolerance and high efficiency.

Photoredox-Controlled ß-Regioselective Radical Hydroboration of Activated Alkenes with NHC-Boranes.

In this Communication, we report an unprecedented ß-regioselective radical inverse hydroboration (compared with ionic hydroboration) of α,ß-unsaturated amides with NHC-BH3 enabled by photoredox catalysis. Density functional theory (DFT) calculations show that the unique photoredox cycle is a key factor to control the ß-regioselective radical hydroboration, by lowering the energy barrier in comparison with other pathways. This protocol provides a general and convenient route to construct a wide range of structurally diverse ß-borylated amides in synthetically useful yields under mild conditions.

Methylenecyclopropane Ring Formation/Opening Cascade for the Synthesis of Indolizines.

A unique strategy toward the synthesis of polysubstituted indolizines has been developed. When 2-pyridinyl-2-(2'-bromoallyl)-1-carboxylates were treated with Cs2CO3, the starting material went through a methylenecyclopropane ring formation/opening cascade, and the corresponding indolizines were obtained in moderate to good yield as a single regioisomer.

Ketosulfonylmethylenation and sulfonylethyleneation of imidazoheterocycles with dimethylformamide as a methylene source.

A hitherto unreported ketosulfonylmethylenation occurring at the C-3 position of imidazoheterocycles, with dimethylformamide as the methylene source was described. Using CoCl2·6H2O or Fe(acac)3 as efficient and inexpensive catalysts, some important biologically active methylenated compounds were prepared, with high efficacy, favorable functional group compatibilities, and a broad substrate scope.

Construction of a Protoberberine Alkaloid Skeleton via the Palladium-Catalyzed α-Arylation-Amide Formation Cascade.

In this work, we report the strategy of one-pot synthesis of protoberberine alkaloid derivatives via palladium-catalyzed cascade α-arylation and cyclization, which can afford the target molecules in moderate to excellent isolated yields using commercially available raw materials under solvent-free conditions. This protocol provides an efficient and convenient path to multisubstituted protoberberine derivatives. In addition, it can directly afford natural alkaloids.

Photoredox radical borylation of electron-deficient alkenes with NHC-boranes.

An efficient photoredox radical borylation of electron-deficient Morita-Baylis-Hillman type alkenes is achieved to afford multi-functionalized allylic boranes. The reaction demonstrates a wide substrate scope and showcases excellent functional group tolerance. It has advantages over the traditional ionic hydroboration methods in the construction of allylic boranes in terms of simple operation, mild conditions, and step-economy.