Palladium-catalyzed oxidative arylacetoxylation of alkenes: synthesis of indole and indoline derivatives.

A method for the oxidative arylacetoxylation of alkenes has been developed to synthesize indole and indoline derivatives from readily accessible substrates. The cinnamyl tethered anilines with picolinamide as a directing group provided 3-substituted indoles via intramolecular oxidative arylacetoxylation, and the 2-methyl substituted cinnamyl anilines furnished indoline derivatives with 3-position quaternary stereocenters in good to excellent yields via sequential intramolecular oxidative arylacetoxylation, hydrolysis and oxidation steps.

Synthesis of Spiro-dihydroquinoline and Octahydrophenanthrene Derivatives via Palladium-Catalyzed Intramolecular Oxidative Arylation.

A method for intramolecular sp C-H oxidative arylation of unactivated cyclic olefins has been developed to access spiro-dihydroquinoline and octahydrophenanthrene derivatives in a straightforward and efficient manner. Bearing picolinamide as a directing group, the alkenyl anilines cyclized to afford spiro-dihydroquinolines in moderate to excellent yields via direct oxidative arylation, while the alkenyl benzylamines furnished the octahydrophenanthrene derivatives in moderate yields via sequential oxidative arylation and double acetoxylation.

Catalytic Multisite-Selective Acetoxylation Reactions at sp vs sp C-H Bonds in Cyclic Olefins.

The first Pd-catalyzed multisite-selective acetoxylation reactions are disclosed at an unactivated alkene sp C-H bond versus secondary allylic sp C-H bond in cyclic olefins via the modulation of directing groups. The different directing groups overcome the key challenge in differentiating C-H bonds and provide a new controlling approach for site-specific C-H activation. A wide variety of substrates are readily acetoxylated under operationally simple conditions.