Two δ-iodo-γ-lactones and two γ-iodo-δ-lactones substituted at the β-position with phenyl or 4-methylphenyl ring have been synthesized in both enantiomeric forms. The starting materials were enantiomerically enriched allyl alcohols with an ( E)-4-phenylbut-3-en-2-ol system ( ee in the range 88-99 %), which were obtained by lipase-catalyzed transesterification. Alcohols were subjected to orthoacetate modification of the Claisen rearrangement. The high stereoselectivity of this reaction led to retention of ( E)-configuration of the double bond and complete transfer of chirality from the allyl alcohol to the benzylic position C-3. As a result, chiral γ,δ-unsaturated esters with retained configuration of the stereogenic center were produced. Their hydrolysis and iodolactonization afforded new enantiomers of iodolactones with high or excellent ee (97-99 %). Their configuration at C-4 was a direct result of the configuration at C-3 of the acid subjected to iodolactonization, whereas stereocenters at C-5 and C-6 were formed as a consequence of the reaction mechanism. For most of the synthesized isomers, the predicted configurations were established by X-ray analysis. The presented chemoenzymatic pathway represents a useful strategy that can be applied in the asymmetric synthesis of variety of lactones from 4-arylbut-3-en-2-ols. [ABSTRACT FROM AUTHOR]