George, JosemonWard, JasSherburn, Michael2020-09-042020-09-042041-6520http://hdl.handle.net/1885/209329The first general synthetic approach to substituted [3]- and higher dendralenes is reported. Fifty-one monothrough to penta-substituted dendralenes carrying alkyl-, cycloalkyl-, alkenyl-, alkynyl-, aryl- and heteroaryl-substitutents are accessed, and the first (E)/(Z)-stereoselective syntheses of dendralenes are reported (twenty-eight examples). The approach involves twofold Pd(0)-catalyzed Negishi couplings of 1,1-dibromoalkenes with alkenylzinc reagents, and exploits both substrate- and catalyst-controlled aspects of chemo-, regio- and stereoselectivity in the two C(sp2 )–C(sp2 ) bond forming steps. The value of the new hydrocarbons in rapid structural complexity generation is demonstrated through their deployment in unprecedented diene- and triene-transmissive pericyclic reaction sequences.application/pdfen-AU© The Royal Society of Chemistry 2019https://creativecommons.org/licenses/by/3.0/201910.1039/c9sc03976g2020-05-17Creative Commons Attribution 3.0 Unported Licence.