Datensatz

Zusammenfassung

The fundamental substrate class of α,β-unsaturated esters offers extraordinary synthetic
potential for carbon-carbon bond forming reactions, such as cycloadditions and conjugate
additions, however is rarely applied in asymmetric catalysis due to its relatively low
reactivity. By expanding the concept of silylium-ACDC to non-silicon transfer reactions
(catalytic in silicon), the introduction of chiral C–H acids into asymmetric catalysis and the
identification of two distinct families of imidodiphosphorimidates (IDPi) catalysts, we could
report unprecedented highly enantio- and diastereoselective Diels–Alder and Mukaiyama–
Michael reactions of simple α,β-unsaturated methyl esters. The developed extremely active
chiral Lewis acids represent the most efficient catalysts for asymmetric Diels–Alder reactions
of α,β-unsaturated esters to date while tolerating a very broad scope on a variable scale with
catalyst loadings as low as 0.1 mol%.