Synthesis of Functionalized [3], [4], [5] and [6]Dendralenes through Palladium‐Catalyzed Cross‐Couplings of Substituted Allenoates

A mild method for the synthesis of highly functionalized [3]–[6]dendralenes is reported, representing a general strategy to diversely substituted higher homologues of the dendralenes. The methodology utilizes allenoates bearing various substitution patterns, along with a wide range of boron and alkenyl nucleophiles that couple under palladium catalysis leading to sp‐, sp2‐, and sp3‐substituted arrays. Regioselective transformations of the newly formed unsymmetrical dendralene derivatives are demonstrated. The use of micellar catalysis, where water is the global reaction medium, and room temperature reaction conditions, highlights the green nature of this technology. All from allenes: New technologies for accessing functionalized, symmetrical and unsymmetrical [3] to [6]dendralenes are described. The combination of micellar reaction conditions, low catalyst loadings, and broad substrate compatibility highlights the green and robust nature of the method.