An Expeditious and Atom‐Economical Synthesis of a New Generation of Substituted [4.6.4.6]Fenestradienes

With finesse and strain: Highly strained derivatives of fenestranes, [4.6.4.6]fenestradienes, have been prepared using a remarkable reaction cascade featuring a 4-exo-dig cyclocarbopalladation, a Sonogashira-type coupling, a regioselective alkynylation, and an 8π/6π electrocyclization sequence.