Diarylmethanones react readily with DMF when promoted by samarium metal in DMF with TMSCl or iodine as an activator, to afford benzoins in good to excellent yields via rearrangement of aryl groups. As for asymmetric diarylmethanones, products resulting from the migration of either aryl group were obtained, where the migration of aryl groups shows certain priority.

Abstract—Promoted by samarium metal in DMF and in the presence of TMSCl, 1,1-diaryl-2, 2-dicyanoethylenes undergo an unexpected kind of reductive cyclization, thus affording a new approach to the construction of indene core. Simultaneously, disilylation occurred at the amino moiety resulting from the reduction of the cyano group.

Promoted by samarium metal in DMF, aroyl chlorides react readily with iso-pentylene in a four-molecule manner, which offers an efficient stereo-and regiospecific synthesis of (E)-β,γ-unsaturated carbonyl compounds and also provides a facile method for the construction of monoterpene skeleton. The reaction is an additional example of organic reactions mediated by direct use of unactivated metallic samarium.

Promoted by samarium in DMF, arenesulfonyl chlorides can be selectively reduced to diaryldisulfones, diarylthiosulfonates and diaryldisulfides in good to excellent yields by reaction temperature control without the need to pretreat or activate the metallic samarium.

Promoted by samarium in DMF, aroyl chlorides react readily with conjugated carbon-carbon double bonds in acrylates, acrylamides, methyl vinyl ketone and styrenes in a bis-acylation manner. These reactions proceed smoothly under mild conditions without the need of pretreating or activating the metallic samarium, affording the corresponding 1,4-diketones in good to excellent yields.