American Chemical Society
jo2c00889_si_004.pdb (12.39 kB)

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

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posted on 2022-06-06, 14:03 authored by Ravindra D. Aher, Atsuhiro Ishikawa, Masahiro Yamanaka, Fujie Tanaka
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.