Poly(lactide) (PLA) is the most well known biodegradable and biocompatible material among the aliphatic polyesters nowadays explored for biomedical, pharmaceutical and environmental applications. Different poly(lactide)s are distinguished, namely stereoregular PLLA and PDLA, atactic, heterotactic, syndiotactic and stereoblock PLAs. Because the stereochemistry of the monomeric units in the polymer chains plays a decisive role in the mechanical, physical and degradation properties of PLA materials, stereospecific catalysts to prepare different polylactide architectures are a major topic. In this review, after a general introduction on metal catalyzed ring opening polymerization, we mainly focus on single site catalyst systems inducing stereoselective polymerization of lactides.

A series of aluminum ethyls and isopropoxides based upon N,N,O,O-tetradentate Schiff base ligand framework have been prepared. X-ray diffraction analysis and 1 H NMR confirmed that these Schiff base aluminum ethyls and isopropoxides were all monomeric species with a five-coordinated central aluminum in their solid structures. Compared to the aluminum ethyls which all retain their monomeric structure in the solution, the dinucleating phenomenons of aluminum isopropoxides with less steric hindered substituents in the solution have also been observed. The activities and stereoselectivities of these complexes toward the ring-opening polymerization of rac-lactide have been investigated. Polymerization experiments indicated that (SB-2d)AlO i Pr [(SB-2d) ) 2,2dimethyl-1,3-propylenebis(3,5-di-tert-butylsalicylideneiminato)] exhibited the highest stereoselectivity and (SB-3b)AlO i Pr [(SB-3b) ) 2,2-dimethyl-1,3-propylenebis(3,5-dichlorinesalicylideneiminato)] possessed the highest activity among these aluminum isopropoxides. The substituents and the mode of the bridging part between the two nitrogen atoms both exerted significant influences upon the progress of the polymerizations, influencing either the tacticity of isolated polymers or the rate of polymerization. The polymerization kinetics using (SB-3b)AlO i Pr as a catalyst were studied in details, and the experimental results revealed that the rate of polymerization was first-order in [LA] and 1.81th-order with respect to (SB-3b)AlO i Pr, which indicated that the propagating species was not uniform in the system without the protection of steric hindered substituents. Furthermore, the polymerization by initiating with (SB-3b)AlO i Pr could be progressed at low temperatures (0 °C) without the change of stereoselectivity.

Synthetic routes to aluminium ethyl complexes supported by chiral tetradentate phenoxyamine (salan-type) ligands [Al(OC(6)H(2)(R-6-R-4)CH(2))(2){CH(3)N(C(6)H(10))NCH(3)}-C(2)H(5)] (4, 7: R=H; 5, 8: R=Cl; 6, 9: R=CH(3)) are reported. Enantiomerically pure salan ligands 1-3 with (R,R) configurations at their cyclohexane rings afforded the complexes 4, 5, and 6 as mixtures of two diastereoisomers (a and b). Each diastereoisomer a was, as determined by X-ray analysis, monomeric with a five-coordinated aluminium central core in the solid state, adopting a cis-(O,O) and cis-(Me,Me) ligand geometry. From the results of variable-temperature (VT) (1)H NMR in the temperature range of 220-335 K, (1)H-(1)H NOESY at 220 K, and diffusion-ordered spectroscopy (DOSY), it is concluded that each diastereoisomer b is also monomeric with a five-coordinated aluminium central core. The geometry is intermediate between square pyramidal with a cis-(O,O), trans-(Me,Me) ligand disposition and trigonal bipyramidal with a trans-(O,O) and trans-(Me,Me) disposition. A slow exchange between these two geometries at 220 K was indicated by (1)H-(1)H NOESY NMR. In the presence of propan-2-ol as an initiator, enantiomerically pure (R,R) complexes 4-6 and their racemic mixtures 7-9 were efficient catalysts in the ring-opening polymerization of lactide (LA). Polylactide materials ranging from isotactically biased (P(m) up to 0.66) to medium heterotactic (P(r) up to 0.73) were obtained from rac-lactide, and syndiotactically biased polylactide (P(r) up to 0.70) from meso-lactide. Kinetic studies revealed that the polymerization of (S,S)-LA in the presence of 4/propan-2-ol had a much higher polymerization rate than (R,R)-LA polymerization (k(SS)/k(RR)=10.1).