Catalytic Enantioselective Construction of Decalin Derivatives by Dynamic Kinetic Desymmetrization of C2-Symmetric Derivatives through Aldol–Aldol Annulation

We have developed and investigated
a catalytic desymmetrization
reaction strategy that affords functionalized decalin derivatives
with high enantioselectivities from C2-symmetric derivatives through
aldol–aldol annulation. We identified the structural moieties
of the catalyst necessary for the formation of the decalin derivative
with high enantioselectivity. We elucidated the mechanisms of the
catalyzed reactions: the first aldol reaction step was reversible,
and the second aldol step was rate-limiting and stereochemistry-determining
and was enantioselective. Using theoretical calculations guided by
the experimental results, we identified the interactions between the
catalyst and the transition state that led to the major enantiomer.
The information obtained in this study will be useful for the development
of catalysts and chemical transformations.