Stereochemistry of lactide polymerization with chiral catalysts: new opportunities for stereocontrol using polymer exchange mechanisms.
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.
Ovitt
Tina M
TM
Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853-1301, USA.
Coates
Geoffrey W
GW
D000535:Aluminum / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011091:Polyesters / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D015018:Ytterbium / Q000737:chemistry*
D009942:Organometallic Compounds; D011091:Polyesters; C033616:poly(lactide); D000535:Aluminum; D015018:Ytterbium