Acylsilane represents one valuable synthon in synthetic chemistry. We report on ruthenium(II)-catalyzed ortho-C−H amination of aroylsilanes to provide facile access toward synthetically useful imidobenzoylsilanes and tosyl-amidobenzoylsilanes. The protocols, occurred with...

A practical and atom-economic protocol for the stereoselective preparation of various 1,4-and 1,3-diene skeletons through iridium-catalyzed directed olefinic C−H allylation and alkenylation of NH-Ts acrylamides in water was developed. This reaction tolerated a wide scope of substrates under simple reaction conditions and enabled successful gram-scale preparation. Furthermore, an asymmetric variant of this reaction giving enantioenriched 1,4-dienes was achieved employing a chiral diene−iridium complex as the catalyst.

A ruthenium-catalyzed [1,2]-Brook rearrangement involved domino sequence is presented to prepare highly functionalized silyloxy indenes with atomic- and step-economy. This domino reaction is triggered by acylsilane-directed C–H activation, and the aldehyde controlled the subsequent enol cyclization/Brook Rearrangement other than β–H elimination. The protocol tolerates a broad substitution pattern, and the further synthetic elaboration of silyloxy indenes allows access to a diverse range of interesting indene and indanone derivatives.