Functional Mechanically Interlocked Molecules: Asymmetric Organocatalysis with a Catenated Bifunctional Brønsted Acid

Abstract

Interlocked molecules, such as catenanes, rotaxanes, and molecular knots, have become interesting candidates for the development of sophisticated chemical catalysts. Herein, we report the first application of a catenane-based catalyst in asymmetric organocatalysis, revealing that the catenated catalyst shows dramatically increased stereoselectivities (up to 98 % ee) in comparison to its non-interlocked analogues. A mechanistic rationale for the observed differences was developed by DFT studies, suggesting that the involvement of two catalytically active groups in the stereodetermining reaction step is responsible for the superior selectivity of the interlocked catalyst.

Keywords: catenanes; density functional calculations; organocatalysis; reaction mechanisms; supramolecular catalysis.