Sonogashira‐type cross‐couplings are one of the most significant alkynylations in organic chemistry. One of the first palladium‐catalyzed intramolecular Heck/Sonogashira reactions of alkenes with terminal alkynes is now reported. With this method, a variety of uniquely substituted chiral benzene‐fused heterocycles bearing a propargyl‐substituted all‐carbon quaternary stereocenter were obtained in a straightforward, high‐yielding, and highly stereoselective manner under mild conditions. Salient features of this process include the use of readily available substrates, high selectivities, a broad substrate scope as well as versatile product functionalizations.

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A Pd/Xu-Phos-catalyzed asymmetric Heck/Suzuki domino reaction has been developed that shows high functional group tolerance and enables coupling with various aryl/alkenyl borates. A series of chiral disubstituted dihydroisoquinolinones could be obtained in good yields and excellent enantioselectivities.

Polycyclic polyprenylated acylphloroglucinols (PPAPs) share a common bicyclo[3.3.1]­alkenone core structure and attract numerous attention from synthetic organic chemists due to their fascinating biological properties and associated synthetic challenges. We present herein that Pd-phosphoramidite catalysts promote the enantioselective dearomative allylic annulation reaction between allyl desoxyhumulones and allylic dicarbonates, affording PPAPs analogues in good yields and enantioselectivities. The reaction likely proceeds through two-step dearomative allylation by Pd, and the C-allylation pathway is the dominant mechanistic model.

γ‐Butenolide and γ‐butyrolactone scaffolds are two types of important core structures in numerous natural products and bioactive targets. However, methods to construct the chiral quaternary arylated γ‐butenolide are rarely explored. We herein report an efficient Pd‐catalyzed enantioselective γ‐arylation of β,γ‐unsaturated butenolides with aryl bromides, which shows high γ‐selectivity, good functional group tolerance and excellent enantioselectivity. Notably, this protocol also allows for facile construction of tricyclic tetrahydroindolines and tetrahydroisoquinolinones in one step. DFT calculations are consistent with the experimental results, suggesting that the γ‐arylation is favoured over the α‐arylation. Finally, this method is applied to the rapid synthesis of natural product (R)‐(+)‐boivinianin A.