The enantioselective synthesis of α-chlorinated
carboxylic
acid esters with er up to 99:1 and yields up to 82% was achieved via
a one-pot multistep protocol starting from α-diazoketones. This
process proceeds via a photochemical Wolff rearrangement, trapping
of the generated ketene with a chiral Lewis base catalyst, subsequent
enantioselective α-chlorination, and a final nucleophilic displacement
of the bound catalyst. The obtained products were successfully utilized
for stereospecific nucleophilic displacement reactions withN- andS-nucleophiles.