A reaction of dithiocarbamic acid salts with carbonyl compounds was investigated for the first time in the presence of BF(3)·OEt(2). The reaction is temperature dependent and gives gem-bis(dithiocarbamates) at 35-45 °C as a molecule with high equivalents of dithiocarbamate groups. At lower temperatures (15-20 °C), the 2-iminium-1,3-dithietane is obtained as the only product. The structure of a 2-iminium-1,3-dithietane was accomplished by X-ray crystallographic analysis.

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Ligand-controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo-and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre-catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2-semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3semireduction, producing (E)-enamide derivatives.

Etherate. -The title synthesis is advantageous with regards to high yields, mild reaction conditions and good functional group tolerance. Products (IVe,f) decompose within one day. -(NEMATI*, F.; GHARJEH GHIYAEI, A. G.; NOTASH, B.; SHAYEGAN, M. H.; AMANI, V.; Tetrahedron Lett. 55 (2014) 25, 3572-3575, http://dx.