Precision synthesis of optically active poly(lactic‐alt‐caprolactic acid) is realized using cross‐metathesis polymerization (CMP) and hydrogenation. Enantiopure monomers ML and MD are generated through two consecutive esterification reactions. CMP of these two monomers in different feed ratios, followed by hydrogenation, afford saturated polymers HPL, HPD, and HPDL comprising L‐lactic and/or D‐lactic acid and ε‐caprolactone‐derived motifs with alternating sequences. CMP kinetic analysis by nuclear magnetic resonance (NMR) is performed by employing a racemic monomer Mrac. Enantiomeric polyesters HPL and HPD display opposite rotation values and mirror‐imaged cotton effects in circular dichroism (CD) spectra, whereas HPDL derived from equimolar ML and MD shows inactive optical rotation and no CD response. Stereocomplex HPD+HPL is obtained by equimolar mixing of HPL and HPD, since this specimen is the only one to exhibit a sharp melting peak on differential scanning calorimetry (DSC) curve at 45.7 °C. Hence, an amorphous, enantiomerically pure polyester becomes crystalline via stereocomplexation with its complementary enantiomer.
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