Beschreibung:
<jats:title>Abstract</jats:title><jats:p>An organocatalytic modified Pudovik reaction between dialkyl or diaryl phosphites and α‐haloketones was used to synthesize β‐chloro‐α‐hydroxyphosphonates in high yields with very high regioselectivity and high stereoselectivity. Aliphatic, aromatic, and cyclic ketones could be used successfully. Under the optimized conditions it was possible to obtain enantiomerically enriched products with a combination of quinine and a stoichiometric racemic base, but the <jats:italic>ee</jats:italic> values only went up to 40 %. The presence of a β‐chloro functionality allows further synthetic elaboration of the hydroxyphosphonates obtained, which could be useful for target‐oriented synthesis, as these compounds often have important biological activity.</jats:p>