A palladium-catalyzed C−H functionalization/intramolecular asymmetric allylation cascade of N-sulfonyl benzamides with 1,3-dienes has been developed. In the presence of a chiral pyridine−oxazoline ligand, this protocol enables the synthesis of chiral 3,4-dihydroisoquinolones in yields of up to 83% with enantioselectivities of up to 96%, using environmentally friendly air as the terminal oxidant.

A palladium-catalyzed tandem dehydrogenative [4 + 2] annulation of terminal olefins with N-sulfonyl amides via C(sp 2 )−H activation, allylic C(sp 3 )−H activation, and homoallylic C(sp 3 )−H elimination processes has been developed. Promoted by the DMSO ligand, various benzamides, heterocyclic arylamides, alkenyl carboxamides, and commercial olefins are found to be efficient substrates to construct important heterocyclic compounds bearing a vinyl substituent with high E stereoselectivity. Using air as the terminal oxidant also provides a great advantage regarding environmental friendliness.

A palladium-catalyzed cascade reaction of β′-allenoate adducts with aryl/heteroaryl carboxamides through a vinylogous elimination/C−H functionalization/intramolecular allylation reaction sequence has been developed with high Z stereoselectivity. Various ring-fused dihydropyridinones bearing an α,β-unsaturated ester substituent are obtained. It is the first example of application of the allenoate adducts to C−H functionalization annulations as practical precursors of hard-to-get functionalized electron-deficient 1,3-butadienes. Using air as the terminal oxidant also shows a great advantage in environmental friendliness.