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Stereochemistry of Lactide Polymerization with Chiral Catalysts: New Opportunities for Stereocontrol Using Polymer Exchange Mechanisms

2002; American Chemical Society; Volume: 124; Issue: 7 Linguagem: Inglês

10.1021/ja012052+

1943-2984

Tina M. Ovitt, Geoffrey W. Coates,

Organometallic Complex Synthesis and Catalysis

The synthesis of chiral aluminum and yttrium alkoxides and their application for lactide polymerization are reported. The complexes (SalBinap)MOR [4, M = Al, R = (i)Pr; 5, M = Y, R = (CH(2))(2)NMe(2)] are synthesized by reacting the ligand (SalBinap)H(2) [2,2'-[(1,1'-binaphthalene)-2,2'-diylbis(nitrilomethylidyne)]bisphenol] with the appropriate metal trisalkoxide. While enantiomerically pure yttrium complex 5 did not effect stereocontrol in the polymerization of either meso- or rac-lactide, homochiral 4 was found to exhibit excellent stereocontrol in a range of lactide polymerizations. Enantiomerically pure 4 polymerizes meso-lactide to syndiotactic poly(lactic acid) (PLA), while rac-4 polymerizes meso- and rac-lactide to heterotactic and isotactic stereoblock PLA, respectively. On the basis of the absolute stereochemistry of ring-opening of meso-lactide using (R)-4, a polymer exchange mechanism is proposed to account for the PLA microstructures resulting from rac-4.