A broad‐spectrum synthesis of Tetravinylethylenes

The first general synthesis of compounds of the tetravinylethylene (TVE) family is reported. Ramirez‐type dibromo‐olefination of readily accessible penta‐1,4‐dien‐3‐ones generates 3,3‐dibromo[3]dendralenes, which undergo twofold Negishi, Suzuki‐Miyaura or Mizoroki‐Heck reactions with a wide variety of olefinic coupling partners. This route delivers a broad range of unsymmetrically–substituted tetravinylethylenes with up to three different alkenyl substituents attached to the central C=C bond. The extensive scope of the approach is demonstrated by the preparation of the first higher order oligo‐alkenic through‐conjugated/cross‐conjugated hybrid compounds. An unsymmetrically‐substituted TVE is shown to undergo a domino electrocyclization‐cycloaddition with high site‐selectivity and diastereoselectivity, thereby demonstrating the substantial synthetic potential of substituted TVEs for controlled, rapid structural complexity generation.