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A protocol of nucleophilic addition to β-keto esters is reported, aimed to the synthesis of tertiary alcohols with high diastereomeric purity. The combined use of organocerium compounds and TiCl4 makes the procedure very efficient and stereoselective with phenyl ketone derivatives. The effect of the nature of the ester function as well as the group bound to the ketone moiety was investigated and rationalized.

Diastereoselective synthesis of tertiary alcohols by nucleophilic addition to α-substituted-ß-keto esters