Alternating Copolymerization of Epoxides and Anhydrides Catalyzed by Aluminum Complexes

Buchaca, Marc Martínez de Sarasa; Cruz-Martínez, Felipe de la; Martı́nez, Javier; Alonso‐Moreno, Carlos; Fernández‐Baeza, Juan; Tejeda, Juan; Niza, Enrique; Castro‐Osma, José A.; Otero, Antonío; Lara‐Sánchez, Agustín

doi:10.1021/acsomega.8b02759

Cited by 24 publications

(30 citation statements)

References 61 publications

(89 reference statements)

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“…Poly(cyclohexene phthalate) (CHO/PA) was obtained by Ring-Opening Copolymerization (ROCOP) of epoxides and cyclic anhydrides as reported previously (Scheme 1) [35]. Table 1 shows 100% of conversion towards polyesters.…”

Section: Resultsmentioning

confidence: 99%

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Poly(Cyclohexene Phthalate) Nanoparticles for Controlled Dasatinib Delivery in Breast Cancer Therapy

et al. 2019

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The effect on the activity in breast cancer models of the small tyrosine kinase inhibitor dasatinib (DAS), either alone or in combination with other antitumoral agents, has been recently explored. However, DAS is characterized by its low and highly pH-dependent solubility, which could lead to poor uptake of the drug limiting its tumoral efficacy. Thus far, the development of safe and efficient delivery vehicles of DAS to improve the therapeutic efficacy minimizing the toxicity profile is still required. In this work, a biodegradable and biocompatible polyester is assessed, for the first time, as raw material for the generation of polymeric nanoparticles (NPs). NPs of 100 nm with a narrow polydispersity were formulated for the encapsulation of DAS. The enzymatic and cellular degradation of the new drug delivery system has been studied, and the toxicity and blood compatibility evaluated for its potential clinical use. The new material used for the generation of nanoparticles led to encapsulate DAS in an efficient manner with quicker release DAS profile when compared with the FDA-approved biopolymer Polylactide. The new DAS-loaded polymeric nanocarrier gave a superior efficacy when compared to free DAS with no difference in the mechanism of action. The new NPs shown to be a promising DAS delivery system to be further evaluated for breast cancer treatment.

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Section: Resultsmentioning

confidence: 99%

“…Copolymers were carefully washed until SEM-EDX analysis showed no residues of Al catalyst [36]. Microstructural analysis of the copolymer obtained was carried out by nuclear magnetic resonance spectroscopy (see Figure S1 in Supplementary Materials) and size exclusion chromatography [35].…”

Section: Resultsmentioning

confidence: 99%

Poly(Cyclohexene Phthalate) Nanoparticles for Controlled Dasatinib Delivery in Breast Cancer Therapy

et al. 2019

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“…The ROCOP reaction of epoxides and cyclic anhydrides requires the use of a catalyst system, which is usually comprised by a combination of a metal complex and a nucleophile source [15]. A wide range of metal complexes, including chromium [16][17][18][19][20], magnesium [21][22][23], 2 of 13 cobalt [24][25][26][27][28], manganese [26,29,30], iron [31][32][33][34], aluminum [3,[35][36][37][38][39][40] and zinc [41][42][43][44][45][46][47] has been used as catalysts for this process. Most of these complexes required the use of a cocatalyst such as tetrabutylammonium salts (TBAX), bis-(triphenylphospine)iminium salts (PPNX) or 4-dimethylaminopyridine (DMAP) to increase the efficiency and selectivity of the metal complex [15].…”

Section: Introductionmentioning

confidence: 99%

“…The zinc-based complexes displayed good catalytic activity and selectivity for the synthesis of medium molecular weight poly(cyclohexene carbonate) (PCHC) with narrow molecular weight distributions in the absence of a nucleophile as a cocatalyst [52,53]. The use of helical aluminum catalysts for the ROCOP of a range of epoxides and cyclic anhydrides or CHO and CO2 afforded the synthesis of polyester and polyether-polycarbonate materials respectively [36,51]. Furthermore, we have recently reported a new family of acetate Scorpionate aluminum and zinc complexes have been developed as efficient catalysts for the ROCOP of carbon dioxide and epoxides to afford polycarbonates and the terpolymerization reaction of epoxides, cyclic anhydrides and carbon dioxide [3,36,[51][52][53].…”

Section: Introductionmentioning

confidence: 99%

“…The use of helical aluminum catalysts for the ROCOP of a range of epoxides and cyclic anhydrides or CHO and CO2 afforded the synthesis of polyester and polyether-polycarbonate materials respectively [36,51]. Furthermore, we have recently reported a new family of acetate Scorpionate aluminum and zinc complexes have been developed as efficient catalysts for the ROCOP of carbon dioxide and epoxides to afford polycarbonates and the terpolymerization reaction of epoxides, cyclic anhydrides and carbon dioxide [3,36,[51][52][53]. The zinc-based complexes displayed good catalytic activity and selectivity for the synthesis of medium molecular weight poly(cyclohexene carbonate) (PCHC) with narrow molecular weight distributions in the absence of a nucleophile as a cocatalyst [52,53].…”

Section: Introductionmentioning

confidence: 99%

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Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

et al. 2021

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The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

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Bimetallic Al(III) Compounds as Catalysts for the Synthesis of Biodegradable Polyesters and Polycarbonates

et al. 2023

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Ethylenediamine bridged benzoxazine proligands were synthesized by a modified Mannich condensation reaction. The reaction of the proligands with two equivalents of AlMe 3 resulted in the formation of dinuclear Al(III) compounds in high yield and purity. When the ligand binds to the Al(III) center, it forms two separate six-membered N,O-chelates with the two Al atoms that resembles the N-alkylated salan moiety. Each aluminum atom adopts a distorted tetrahedral geometry as revealed from the single-crystal X-ray diffraction studies of 1. The catalytic activity of these aluminum compounds was investigated towards the ROP of rac-LA and ROCOP of epoxides (PO, CHO, tBuGE) and phthalic anhydride and ROCOP of CHO with CO 2 . These aluminum compounds showed notable catalytic activity towards the ROP and ROCOP reactions in the absence of cocatalyst.

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Alternating Copolymerization of Epoxides and Anhydrides Catalyzed by Aluminum Complexes

Cited by 24 publications

References 61 publications

Poly(Cyclohexene Phthalate) Nanoparticles for Controlled Dasatinib Delivery in Breast Cancer Therapy

Poly(Cyclohexene Phthalate) Nanoparticles for Controlled Dasatinib Delivery in Breast Cancer Therapy

Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

Bimetallic Al(III) Compounds as Catalysts for the Synthesis of Biodegradable Polyesters and Polycarbonates

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