Catalytic Asymmetric Synthesis of 2,6‐Disubstituted Cuneanes through Enantioselective Constitutional Isomerization of 1,4‐Disubstituted Cubanes.

2,6‐Disubstituted cuneane has potential as a p‐disubstituted benzene bioisostere and a novel chiral scaffold. It is a constitutional isomer of a 1,4‐disubstituted cubane obtained via a metal‐catalyzed skeletal rearrangement. Unlike the highly symmetrical 1,4‐disubstituted cubane, the isomerized 2,6‐disubstituted cuneane is a chiral molecule possessing C2 symmetry. Examining various chiral catalysts revealed that the Pd‐pincer catalyst provides a good asymmetric induction. [ABSTRACT FROM AUTHOR]