Functionalization of activated methylene C-H bonds with nitroarenes and sulfur for the synthesis of thioamides.

We report a method to obtain arylthioamides by the functionalization of sp3 C-H bonds in phenylacetic acids and benzyl alcohols. Reactions proceeded without the use of any solvents and were compatible with many functionalities and heterocycles. These conditions allow for a rapid synthesis of thioamides from simple, commercial substrates.

A new route to substituted furocoumarins via copper-catalyzed cyclization between 4-hydroxycoumarins and ketoximes.

A new route to substituted furocoumarins via copper-catalyzed cyclization between 4-hydroxycoumarins and ketoximes was developed. CuBr2 exhibited higher activity than other copper salts, affording the desired furocoumarins in high yields. The transformation proceeded readily in the absence of stoichiometric external oxidants. The significance of this synthetic strategy would be (1) the easily available starting materials; (2) low cost catalyst CuBr2; and (3) being without stoichiometric external oxidants. This protocol is complementary to previous approaches in the synthesis of substituted furocoumarins.

Cobalt-catalyzed annulation of styrenes with α-bromoacetic acids.

We report a method for addition of α-bromophenylacetic acids to vinyl C[double bond, length as m-dash]C bonds in styrenes to afford γ-lactones. Reactions employed a simple cobalt catalyst Co(NO3)2·6H2O in the presence of dipivaloylmethane (dpm) ligand. Many functionalities including halogen, ester, and nitro groups were compatible with reaction conditions. If α-bromoesters were used, vinylacetates were the major products.

Synthesis of primary N-arylthioglyoxamides from anilines, elemental sulfur and primary C-H bonds in acetophenones.

A simple method for coupling of anilines, acetophenones, and elemental sulfur to afford N-arylthioglyoxamides has been developed. Reactions proceeded in the presence of Na2SO3 and DMSO, thus eliminating the need for transition metals and external oxidants. Functionalities such as halogen, ester, methylthio, and heterocycle groups were compatible with the conditions. Electron-poor acetophenones sometimes gave isosteric glyoxamides.

An efficient access to ß-ketosulfones via ß-sulfonylvinylamines: metal-organic framework catalysis for the direct C-S coupling of sodium sulfinates with oxime acetates.

A copper-based framework Cu2(OBA)2(BPY) was synthesized and used as a recyclable heterogeneous catalyst for the synthesis of ß-sulfonylvinylamines from sodium sulfinates and oxime acetates via direct C-S coupling reaction. The transformation was remarkably affected by the solvent, and chlorobenzene emerged as the best option. This Cu-MOF displayed higher activity than numerous conventional homogeneous and MOF-based catalysts. The catalyst was reutilized many times in the synthesis of ß-sulfonylvinylamines without considerably deteriorating in catalytic efficiency. These ß-sulfonylvinylamines were readily converted to the corresponding ß-ketosulfones via a hydrolysis step with aqueous HCl solution. To the best of our knowledge, this direct C-S coupling reaction to achieve ß-sulfonylvinylamines was not previously conducted with a heterogeneous catalyst.