Here, we present
a new stereoselective alkylation of titanium(IV)
enolates of chiral
N
-acyl oxazolidinones with
tert
-butyl peresters from Cα-branched aliphatic carboxylic
acids, which proceeds through the decarboxylation of the peresters
and the subsequent formation of alkyl radicals to produce the alkylated
adducts with an excellent diastereoselectivity. Theoretical calculations
account for the observed reactivity and the outstanding stereocontrol.
Importantly, the resultant compounds can be easily converted into
ligands for asymmetric and catalytic transformations.