posted on 2023-11-17, 21:09authored byKenta Iizuka, Hiroki Takezawa, Makoto Fujita
Desymmetrization
of a symmetric skeleton enables late-stage
functionalization
of molecules. However, reagent-controlled desymmetrization by site-selective
reactions of symmetric molecules remains a difficult synthetic strategy.
Here, we found that complete confinement of a symmetric molecule within
a coordination cage can desymmetrize the guest conformation, making
it possible to site-selectively activate or protect the otherwise
equivalent reaction sites of calix[4]arene derivatives. Multistep,
one-cage reactions also demonstrated the transformation of an AAAA-type
calix[4]arene into a lower symmetry ABAC-type one.