Multicomponent Synthesis of 3,6-Dihydro-2H-1,3-thiazine-2-thiones

Non-fused 3,6-dihydro-2H-1,3-thiazine-2-thiones constitute a so far rather unexplored class of compounds, with the latest report dating back more than two decades. Thiazine-2-thiones contain an endocyclic dithiocarbamate group, which is often found in pesticides, in substrates for radical chemistry and in synthetic intermediates towards thioureas and amidines. We now report the multicomponent reaction (MCR) of in situ-generated 1-azadienes with carbon disulfide. With this reaction, a one-step protocol towards the potentially interesting 3,6-dihydro-2H-1,3-thiazine-2-thiones was established and a small library was synthesized

Mechanistic Investigations of Nickamine-catalyzed Hydrosilylation of Alkenes: Nickel Nanoparticles Are the Active Species

Hydrosilylation is an important chemical process for the synthesis of organosilanes and for the production of silicone polymers. The wide variety of catalysts developed for this reaction generally follow a Chalk-Harrod, or a sigma-bond metathesis mechanism. Recently, our group developed a nickel pincer complex, Nickamine, for highly selective hydrosilylation of alkenes. Preliminary mechanistic studies had suggested a pathway that deviates from both Chalk-Harrod and sigma-bond metathesis cycles. Here we used in situ NMR to monitor the hydrosilylation reaction. The observed induction period indicated that the species previously believed to be the resting state is merely a precatalyst. Via a combination of Transmission Electron Microscopy, mercury poisoning test, and competition reactions we show that the true catalyst is not a molecular nickel species, but rather nickel nanoparticles

Reductive Cleavage of Azoarene as a Key Step in Nickel-Catalyzed Amidation of Esters with Nitroarenes

status: publishe