Palladium‐Catalyzed Tunable Carbonylative Synthesis of Enones and Benzofulvenes

A palladium‐catalyzed four‐component carbonylative coupling reaction involving aryl halides, internal alkynes, arylboronic acids, and CO has been developed for the first time. All‐carbon substituted α‐unsaturated ketones and benzofulvenes can be selectively obtained in a highly regio‐ and stereocontrolled manner. Using Cu(TFA) 2 as the additive, a series of tetrasubstituted α‐unsaturated ketones were prepared in moderate to high yields. Using more acidic Lewis acid Cu(OTf) 2 as the additive, multisubstituted benzofluvenes were synthesized in moderate yields. This efficient methodology involved the formation of three new C−C bonds, and provided a divergent method for the quick construction of multisubstituted α‐unsaturated ketones and benzofulvenes from easily available starting materials.