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Development of the efficient initiators of ring-opening polymerization (ROP) of cyclic esters (lactide, glycolide, ε-caprolactone) is one of the important trends of modern chemistry. Usually organometallic compounds used as initiators of this process. Aluminum complexes based on phenolate ligands are easily accessible, their catalytic behavior in ROP is studied in detail. In accordance with coordination/insertion mechanism of ROP, the fragment of alcohol originally present in molecule of initiator is transferred to the end of the polymer chain. In this respect we proposed that application of aluminum complexes containing at Al atom fragments of unsaturated alcohols as initiators of ROP will results to macromonomers, which may be used as precursors of more complicated biodegradable polymer structures (brushes, stars etc.) In this work we describe the synthesis of several aluminum complexes containing fragments of unsaturated alcohols (5, 6). The compounds 5, 6 were investigated by multinuclear NMR spectroscopy and X-ray analysis. Compounds 5, 6 have high activity in ROP of D, L-lactide and ε-caprolactone. The corresponding macromonomers were obtained with high functionality.