<i>o</i> ‐Quinodimethane Atropisomers: Enantioselective Synthesis and Stereospecific Transformation

o-Quinodimethanes have remarkable utility as reactive intermediates in Diels–Alder reactions, enabling significantly accelerated routes to complex polycyclic compounds. The discovery of different discrete precursors thermally generate o-quinodimethanes thereby greatly augmented their availability and versatility. However, due the required high temperatures immense reactivity o-quinodimethanes, stereoselectivity afford isomerically defined products still constitutes a critical challenge. Herein, we describe accessibility atropisomeric enantioselective synthesis precursors, configurational stability stereospecific transformation by benzannulation dienophiles. A catalyst-stereocontrolled [2+2+2] cycloaddition, generation o-quinodimethane atropisomers ensuing reactions enabled enantioselectivities through these transient with up 96 : 4 e.r.