Ring-opening Polymerization Of Cyclic Esters Research Articles

Synthesis of aluminum complexes supported by 2-(1,10-phenanthrolin-2-yl)phenolate ligands and their catalysis in the ring-opening polymerization of cyclic esters

Phenanthroline-phenolate based N,N,O-chelate aluminum complexes were demonstrated to catalyze the ROP of ε-caprolactone, rac-lactide, and rac-β-butyrolactone, as well as their block copolymerization.

Recent advances in aliphatic polyesters for drug delivery applications.

The use of aliphatic polyesters in drug delivery applications has been a field of significant interest spanning decades. Drug delivery strategies have made abundant use of polyesters in their structures owing to their biocompatibility and biodegradability. The properties afforded from these materials provide many avenues for the tunability of drug delivery systems to suit individual needs of diverse applications. Polyesters can be formed in several different ways, but the most prevalent is the ring-opening polymerization of cyclic esters. When used to form amphiphilic block copolymers, these materials can be utilized to form various drug carriers such as nanoparticles, micelles, and polymersomes. These drug delivery systems can be tailored through the addition of targeting moieties and the addition of stimuli-responsive groups into the polymer chains. There are also different types of polyesters that can be used to modify the degradation rates or mechanical properties. Here, we discuss the reasons that polyesters have become so popular, the current research focuses, and what the future holds for these materials in drug delivery applications. WIREs Nanomed Nanobiotechnol 2017, 9:e1446. doi: 10.1002/wnan.1446 For further resources related to this article, please visit the WIREs website.

The Role of Nitrogen Donors in Zinc Catalysts for Lactide Ring-Opening Polymerization.

The electronic effects of nitrogen donors in zinc catalysts for ring-opening polymerization of cyclic esters were investigated. Alkyl and benzyloxy zinc complexes supported by tridentate diamino- and aminoimino phenolate ligands were synthesized, and their solid-state and solution structures characterized. The solution-state structures showed that the alkyl complexes are mononuclear, while the alkoxy complexes are dimeric with the ligands coordinated with different denticities depending on the nature of the ligand donors. The catalytic activities of these compounds toward the ring-opening polymerization of racemic lactide were studied and showed that catalysts with secondary and imine nitrogen donors are more active than analogues with tertiary amines.

Development and Applications of Transesterification Reactions Catalyzed by N-Heterocyclic Olefins.

A novel method to utilize N-heterocyclic olefins (NHOs), the alkylidene derivatives of N-heterocycic carbenes, as organocatalysts to promote transesterification reactions has been developed. Because of their strong Brønsted/Lewis basicity, NHOs can enhance the nucleophilicity of alcohols for their acylation reactions with carboxylic esters. This transformation can be employed in industrially relevant processes such as the production of biodiesel, the depolymerization of polyethylene terephthalate (PET) from plastic bottles for recycling purposes, and the ring-opening polymerization of cyclic esters to form biodegradable polymers such as polylactide (PLA) and polycaprolactone (PCL).

ChemInform Abstract: Aluminum Alkyl Complexes: Synthesis, Structure, and Application in ROP of Cyclic Esters

AbstractReview: 112 refs.

Aluminum complexes with benzoxazolphenolate ligands: Synthesis, characterization and catalytic properties for ring-opening polymerization of cyclic esters

A family of bidentate ligands, 1–3, were synthesized by the reactions of 5-diethylamino-2-nitrosophenol with bromomethylphenol derivatives. Treatment of the ligands 1–3 with one equivalent of AlMe3 gave the corresponding aluminum complexes 4–6, respectively. All the complexes were characterized by 1H and 13C NMR spectroscopy, along with elemental analysis. Single crystal X-ray diffraction analysis of complex 5 revealed that the Al complex has a distorted tetrahedral geometry around the metal center. All the aluminum complexes are efficient initiators for the ring-opening polymerization of ε-caprolactone and lactide in the presence of benzyl alcohol in a living fashion. The aluminum complexes produced PLA with a slight heterotactic bias.

Structural and kinetic studies of the ring-opening polymerization of cyclic esters using N,N′ diarylformamidines Zn(II) complexes

The reactions of N,N′-bis(2,6-dimethylphenyl)formamidine (L1) and N,N′-bis(2,6-diisopropylphenyl)formamidine (L2), with Zn(OAc)2·2H2O salt and auxiliary benzoate ligands produced the respective Zn(II) formamidine benzoate complexes 1–4. All the complexes were characterized by IR, NMR spectroscopy elemental analysis and single crystal X-ray diffraction analyses for complexes 1, 2 and 3. Complexes 1–4 were active in the ring opening polymerization (ROP) of ɛ-caprolactone (ɛ-CL), d,l-lactide (d,l-LA) and l-lactide (l-LA) monomers. The kinetic results indicated a pseudo-first order dependency on the monomers. The nature of the N,N′ diarylformamidines ligands, auxiliary benzoate and solvent were found to affect the catalytic activity as well as the properties of the polymers. Activation parameters obtained from Eyring plots for the ROP of ɛ-CL using complex 4 points to coordination insertion mechanism.

Strained metal bonding environments in methylindium dithiolates and their reactivity as initiators for the ring-opening polymerization of cyclic esters

We have synthesized indium complexes containing a variety of metal bonding environments through use of polyfunctional dithiolate ligands and examined their reactivity as initiators for the ring-opening polymerization of l-lactide, rac-lactide, ε-caprolactone and β-butyrolactone. The facile reaction of Me3In with the corresponding polyfunctional dithiols in toluene, thf or diethyl ether resulted in the formation of [MeIn(SOOS)]2 (3), MeIn(SNNS) (4), [MeIn(ONS2)]3 (5), MeIn(NNS2) (6), MeIn(NNS2Pr) (7) and MeIn(pyrS)2 (8). The solid-state structures of 3 and 5 each show the corresponding ligand to be tridentate with an uncoordinated ligand O atom. Dimeric (3) and trimeric (5) structures result from short intermolecular In … S interactions. All structures show five coordinate indium centres in distorted trigonal bipyramidal bonding environments, but with various arrangements of donor atoms (eq/ax): SSC/OS (3,5), SNC/NS (4), SSN/NC (6), SSC/NS (7) and SSC/NN (8). DFT studies of model MeIn(SMe)2(NH3)2 systems show the bonding environments in 4 and 6 to be highly strained, while the axial In–Me bond of 6 shows the longest bond distance and lowest vibrational frequency. Compound 5 provided the best control of the polymerization of l-lactide and rac-lactide in THF at 70 °C, and a small heterotactic enrichment was observed for the latter. Compounds 3 and 4 provided the best control of the polymerization of β-BL in toluene at 70 °C in toluene, and compound 3 provided the best control of the polymerization of ε-CL in toluene at 70 °C. In all cases, polymerization rates were low. This work demonstrates a systematic approach to exploring the modification and reactivity of main group metal bonding motifs, which has resulted in identification of two novel “strained” bonding environments for indium.

Aluminum alkyl complexes: synthesis, structure, and application in ROP of cyclic esters

Aluminum alkyl complexes have very useful applications as catalysts or reagents in small molecule transformations and as cocatalysts in olefin polymerization. This short review focuses on some recent developments in the design, synthesis and structure of aluminum(iii) alkyl complexes supported by various ligands bearing nitrogen, oxygen, sulfur or phosphorus atoms, and their catalytic applications in the ring-opening polymerization (ROP) of cyclic esters. The coordination chemistry of the Al metal centre and the catalytic activity changes of the complexes caused by ligand modifications are also discussed.

Metal complexes containing nitrogen-heterocycle based aryloxide or arylamido derivatives as discrete catalysts for ring-opening polymerization of cyclic esters.

The development of well-defined homogeneous catalysts for the ring-opening polymerization (ROP) of cyclic esters has made enormous progress over the past decade. This perspective focuses on some recent advances in the field of discrete metal complexes modified by various aryloxide or arylamido ligands bearing the nitrogen-containing heterocycle moiety, and their catalytic applications in ROP of lactones. It mainly highlights aryloxide/arylamido ligands that are directly installed by the N-heterocyclic group. The complex structure-ROP performance relationships and the observed trends with respect to their catalytic efficiency affected by ligand modifications are also discussed.

ChemInform Abstract: N,O‐Chelating Four‐Membered Metallacyclic Titanium(IV) Complexes for Atom‐Economic Catalytic Reactions

AbstractReview: 66 refs.

Highly Active Yttrium Catalysts for the Ring-Opening Polymerization of ε-Caprolactone and δ-Valerolactone

The activity of several yttrium alkoxide and aryloxide complexes supported by a ferrocene-based ligand incorporating two thiol phenolates, thiolfan (1,1′-bis(2,4-di-tert-butyl-6-thiomethylenephenoxy)ferrocene), was studied. The tert-butoxide complex could only be isolated in the ate form, while a monophenoxide complex could be obtained for OAr = 2,6-di-tert-butylphenolate. The synthetic utility of these yttrium complexes has been demonstrated by the ring-opening polymerization of cyclic esters, with a high activity toward e-caprolactone and δ-valerolactone being found for the yttrium phenoxide complex.

Rare-Earth Complexes Supported by Tripodal Tetradentate Bis(phenolate) Ligands: A Privileged Class of Catalysts for Ring-Opening Polymerization of Cyclic Esters

Tripodal dianionic diamino- or amino-alkoxy-bis(phenolate) ligands {ONXOR1,R2} (X = NR2, OR) constitute a privileged class of ligands which has found much interest in combination with group 3 and group 4 metals for generating highly efficient polymerization catalysts. This account article describes the structural variety of and synthetic routes toward trivalent rare-earth complexes incorporating such {ONXOR1,R2} ancillaries along with reactive amido, alkyl, alkoxide, amidinate, guanidinate, halide, and borohydride groups. The chemistry of related divalent rare-earth complexes is also included. This class of Ln{ONXOR1,R2}(R) complexes features outstanding performance in the ring-opening polymerization (ROP) of cyclic esters. Examples of their high reactivity, which has allowed enlarging the scope of ROP reactions to monomers that are difficult to ring-open, and of their ability to control reactions are provided. A particular emphasis is given on their propensity to fine-tune the stereoselectivity of ROP re...

N,O-Chelating Four-Membered Metallacyclic Titanium(IV) Complexes for Atom-Economic Catalytic Reactions.

Titanium, as the second most abundant transition metal in the earth's crust, lends itself as a sustainable and inexpensive resource in catalysis. Its nontoxicity and biocompatibility are also attractive features for handling and disposal. Titanium has excelled as a catalyst for a broad range of transformations, including ethylene and α-olefin polymerizations. However, many reactions relevant to fine chemical synthesis have preferrentially employed late transition metals, and reactive, inexpensive early transition metals have been largely overlooked. In addition to promising reactivity, titanium complexes feature more robust character compared with some other highly Lewis-acidic metals such as those found in the lanthanide series. Since the advent of modulating ligand scaffolds, titanium has found use in a growing variety of reactions as a versatile homogeneous catalyst. These catalytic transformations include hydrofunctionalization reactions (adding an element-hydrogen (E-H) bond across a C-C multiple bond), as well as the ring-opening polymerization of cyclic esters, all of which are atom-economic transformations. Our investigations have focused on tight bite angle monoanionic N,O-chelating ligands, forming four-membered metallacycles. These ligand sets, including amidates, ureates, pyridonates, and sulfonamidates, have flexible binding modes offering a range of stable and reactive intermediates necessary for catalytic activity. Additionally, the simple form of these ligands leads to easily prepared proligands, along with facile tuning of steric and electronic factors. A sterically bulky titanium amidate complex has proven to be a leading catalyst for the selective formation of anti-Markovnikov addition products via intermolecular hydroamination of terminal alkynes, while sterically less demanding titanium pyridonates have opened the path to the selective formation of amine substituted cycloalkanes via the intramolecular hydroaminoalkylation of aminoalkenes over the competing hydroamination pathway. Sulfonamidates have boosted reactivity for hydrofunctionalization and polymerization reactions compared with amide ligands not bearing a sulfonyl group. N,O-Chelated titanium complexes have been used to synthesize ultrahigh molecular weight polyethylene and have been utilized in the challenging task of realizing equal incorporation of two different cyclic esters in a random ring-opening copolymerization. These discrete complexes have allowed for careful study of fundamental coordination chemistry and stoichiometric organometallic investigations. With inexpensive starting materials and modular ligands, titanium N,O-chelated complexes are well-suited to address the challenges of achieving greener chemical processes while accessing useful reaction manifolds for sustainable synthesis.

Scandium and yttrium phosphasalen complexes as initiators for ring-opening polymerization of cyclic esters.

The synthesis and characterization of novel scandium and yttrium phosphasalen complexes is reported, where phosphasalen refers to two different bis(iminophosphorane) derivatives of the more ubiquitous salen ligands. The activity of the complexes as initiators for the ring-opening polymerization of cyclic esters is presented. The scandium complexes are inactive for lactide polymerization but slow and controlled initiators for ε-caprolactone polymerization. The lack of activity toward lactide exhibited by these compounds is probed, and a rare example of single-monomer insertion product, unable to undergo further reactions with lactide, is identified. In contrast, the analogous yttrium phosphasalen complex is a very active initiator for the ring-opening polymerization of rac-lactide (kobs = 1.5 × 10(-3) s(-1) at 1:500 [yttrium initiator]:[rac-lactide], 1 M overall concentration of lactide in THF at 298 K). In addition to being a very fast initiator, the yttrium complex also maintains excellent levels of polymerization control and a high degree of isoselectivity, with the probability of isotactic enchainment being Pi = 0.78 at 298 K.

Catalytic behaviour in the ring-opening polymerisation of organoaluminiums supported by bulky heteroscorpionate ligands.

A series of alkyl organoaluminium complexes based on bulky heteroscorpionate ligands were designed as catalysts for the ring-opening polymerisation of cyclic esters. Thus, the treatment of AlX3 (X = Me, Et) with bulky acetamide or thioacetamide heteroscorpionate ligands nbptamH (1) [nbptamH = N-naphthyl-2,2-bis(3,5-dimethylpyrazol-1-yl)thioacetamide], fbpamH (2) [fbpamH = N-fluorenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamide], ptbptamH (3) [ptbptamH = N-phenyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)thioacetamide], ntbptamH (4) [ntbptamH = N-naphthyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)thioacetamide], ptbpamH (5) [ptbpamH = N-phenyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)acetamide] and (S)-mtbpamH (6) [(S)-mtbpamH = (S)-(−)-N-α-methylbenzyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)acetamide] for 1 hour at 0 °C afforded the dialkyl aluminium complexes [AlX2{κ(2)-nbptam}] (X = Me 7, Et 8), [AlX2{κ(2)-fbpam}] (X = Me 9, Et 10), [AlX2{κ(2)-ptbptam}] (X = Me 11, Et 12), [AlX2{κ(2)-ntbptam}] (X = Me 13, Et 14), [AlX2{κ2(-)ptbpam}] (X = Me 15, Et 16) and [AlX2{κ(2)-(S)-mtbpam}] (X = Me 17, Et 18). The structures of the complexes were determined by spectroscopic methods and the X-ray crystal structure of 14 was also established. The alkyl-containing aluminium complexes 7–18 can act as efficient single-component initiators for the ring-opening polymerisation of ε-caprolactone and rac-lactide. The polymerisations are living, as evidenced by the narrow polydispersities of the isolated polymers and the linear nature of the number average molecular weight versus conversion plot. Finally, a comparative study of ring-opening polymerisation for new bulky heteroscorpionate aluminium initiators and the less congested aluminium analogues is reported.

Organophosphate-catalyzed bulk ring-opening polymerization as an environmentally benign route leading to block copolyesters, end-functionalized polyesters, and polyester-based polyurethane

To expand the potential of an organophosphate catalyst, ring-opening polymerization of cyclic esters, cyclic ester-ether, and cyclic carbonate was demonstrated under bulk conditions.

Mono-, di- and tetra-zinc complexes derived from an amino-benzotriazole phenolate ligand containing a bulkier N-alkyl pendant arm: synthesis, structure and catalysis for ring-opening polymerization of cyclic esters.

Zinc complexes constructed from the amino-modified benzotriazole phenol pro-ligand, 2-(2H-benzotriazol-2-yl)-6-((diisopropylamino)methyl)-4-(2,4,4-trimethylpentan-2-yl)phenol ((C8DIA)BTP-H, 1), were synthesized stepwise and structurally characterized. The reaction of (C8DIA)BTP-H (1) with one equivalent of diethyl zinc (ZnEt2) generates a dimeric and four-coordinated zinc complex, [(μ-(C8DIA)BTP)ZnEt]2 (2), which is doubly bridged by two phenolate groups of C8DIABTP ligands. Further reaction of 2 with benzyl alcohol (BnOH) in stoichiometric proportions affords a tetranuclear zinc benzylalkoxide complex [(μ-OBn)((C8DIA)BTP)Zn]4 (3) that possesses a saddle-shaped core with four μ2-bridging benzylalkoxy groups upon four Zn centres. Interestingly, the di-nuclear Zn alkoxide [(μ-OBn)((C8DIA)BTP)Zn(DMAP)]2 (4) could be prepared by treatment of 3 with a stoichiometric amount of 4-(dimethylamino)pyridine (DMAP). ZnEt2 reacts with two equivalents of 1 in the presence of DMAP (1.0 mol equiv.) to yield a five-coordinated mononuclear zinc complex, [((C8DIA)BTP)2Zn(DMAP)] (5). All complexes adopt an N,O-bidentate coordination mode from the phenoxy oxygen atom and benzotriazole nitrogen atom, in which the nitrogen atom of the pendent arm substituent is not coordinated to the zinc centre. Ring-opening polymerization of ε-caprolactone and β-butyrolactone catalysed by 2 and 3 was investigated.

Zinc complexes coordinated by bipyridine-phenolate ligands as an efficient initiator for ring-opening polymerization of cyclic esters

A series of zinc complexes coordinated by different bipyridine-phenolate (BpyPh) ligands, 2-([2,2′-bipyridin]-6-yl)-4,6-di-tert-butylphenol (BpyPh2,4-tBu-H, 3) and 2-([2,2′-bipyridin]-6-yl)-4-(tert-butyl)phenol (BpyPh4-tBu-H, 4) have been synthesized. The reaction of BpyPh2,4-tBu-H with ZnEt2 gave a six-coordinated complex of [(BpyPh2,4-tBu)2Zn] (5) with the distorted octahedral geometry. However, the dinuclear complexes of [(BpyPh)Zn(μ-OBn)]2 (6 and 7) were formed when benzyl alcohol was added and then can be converted to mononuclear zinc benzylalkoxide species by the increased temperature. The ε-CL and L-LA polymerizations initiated by complex 6 showed the living characteristics of narrow molecular weight distribution (PDIs < 1.15) and the capability of block copolymer synthesis demonstrated by the formation of PCL-b-PVL and PCL-b-PHB. The ring-opening polymerizations of cyclic esters initiated by complex 5, however, was not effective possibly due to the highly steric hindered metal center.

Dinuclear zinc complexes with chiral tetra-azane ligands: Synthesis, structures and catalytic properties for ring-opening polymerization of cyclic esters

Reactions of chiral tetra-azane chelating ligands (1R,2R)-[(NHAr)C6H4CHN]2C6H10 (L1H2 (Ar=2,6-iPr2C6H3); L2H2 (Ar=2,6-Et2C6H3); L3H2 (Ar=2,6-Me2C6H3) with 2 equivalents of ZnMe2 to afford the dinuclear zinc complexes (L1Zn2Me2(1), L2Zn2Me2(2), L3Zn2Me2(3)), respectively. These complexes were characterized by 1H and 13C NMR spectroscopies and elemental analyses. Single crystal X-ray diffraction analyses reveal that complex 1 adopts a trigonal planar geometry around the Zn centers. Subsequent investigations showed that all the zinc complexes were efficient catalysts for the ring-opening polymerization of cyclic esters in the presence of benzyl alcohol in a controlled fashion.