A chiral anion-mediated asymmetric Heck/Tsuji–Trost reaction of aryl iodides and 1,3-dienes is presented. Chiral indoline derivatives could be afforded with remarkably higher yields and enantioselectivities than our previous chiral ligand-based method. Silver carbonate is employed as both base and halide scavenger to ensure fast and recyclable exchange of the catalytic amount of chiral anions. Fast salt metathesis, as well as the acceleration effect of the chiral anion, could both benefit the stereocontrol of the reaction.

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A photoinduced palladium-catalyzed cascade reaction involving remote C(sp3)−H functionalization and intramolecular Tsuji-Trost annulation is developed. The reaction is proposed to proceed through a sequence involving the amidyl radical generation, 1,5-HAT mediated alkyl radical formation and subsequent difunctionalization of 1,3-dienes. Without the use of exogeneous photosensitizers and external oxidants, the reaction provided an efficient approach to multi-substituted chiral piperidines in high yields, employing readily available chiral amino acid derivatives and 1,3-dienes as the substrates. In most cases, the syn/anti ratio of the product could be further improved by treatment with catalytic amount of iron salt.