Dialkylgallium alkoxides – a tool for facile and stereoselective synthesis of PLA–drug conjugates

Cybularczyk‐Cecotka, Martyna; Zaremba, Rafał; Hurko, Aleksander; Plichta, Andrzej; Dranka, Maciej; Horeglad, Paweł

doi:10.1039/c7nj03089d

Cited by 4 publications

(3 citation statements)

References 26 publications

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“…Alkoxide bases were used as catalysts for the aza-Michael reaction, KOH, NaOH, NaOC(CH 3 ) 3 , KOC(CH 3 ) 3 , NaOCH 3 , KOCH 3 , and CH 3 COONa (as shown in Table 1). [38][39][40][41] The strong bases NaOH and KOH showed less catalytic reactivity, and the trifunctional structure of itaconic acid ensured that the reactivity of carboxylic acid and unsaturated bond differed. The itaconic acid and amino acidbased heterocyclic diacid developed after the reaction of the alkene group of itaconic acid with the amine group of the amino acid.…”

Section: Synthesis Of Chiral Diacidmentioning

confidence: 99%

“…Alcohols are weak acids, while the sodium and potassium salts of alcohol easily dissociate in the reaction solution with alkoxides as conjugate bases. [38][39][40][41] The alkoxides abstract hydrogen from the amino acid after reaction with a nucleophile and directly react with the unsaturated double bond of itaconic acid. This forms a resonant-stabilized intermediate enolate with electronegative oxygen, which was subsequently protonated to form a ketone.…”

Section: Synthesis Of Chiral Diacidmentioning

confidence: 99%

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High‐Performance BioNylons from Itaconic and Amino Acids with Pepsin Degradability

Ali

Kaneko

2021

Advanced Sustainable Systems

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dianhydro-d-mannitol (isomannide), and 1,4,3,6-dianhydro-l-iditol (isoidide). [5][6][7][8] However, low T g values of biobased polyamides restrict their application. [3][4][5][6][7][8] On the other hand, considerable progress has been made in the syntheses of enantiomeric d-and l-poly(hexamethylene di-Omethyltartaramide)s {P6DMT(d-/l-)} a pair of stereoregular polyamides is reported. [9][10][11] The (+)-3-carene based chiral polyamides such as poly-3R-caranamide and poly-3S-caranamide have high T g (70-100 °C). [2] Besides, terpenes-based chiral polyamide, which were derived from (R)-(+)-, (S)-(-)limonene, and (-)-β-pinene showed the T g value in the range of 40-42 °C. [2,12,13] Enhancement of interchain interaction based on chirality should be effective on increasing the softening temperature of the polymers. The polyamides have a synergistic effect on chiral interaction and hydrogen bonding between the different moieties. [11,14,15] Recently, we have reported the preparation of polyamides with heterocyclic amide ring such as pyrrolidone to increase the T g , owing to the rigidity and interchain hydrogen bonding. [16][17][18] The pyrrolidone ring was derived from itaconic acid (IA), which is a notable bio-renewable resource that can be mass-produced from Aspergillus terreus via fermentation using glucose. [17][18][19] IA reacted with amine compounds through its corresponding salt monomer to form heterocyclic pyrrolidone by aza-Michael addition of amines to IA's double bond successive ring-closing condensation with a carboxylic acid upon heating. [20,21] N-substituted amide linkage restricts water absorption, which can contribute to reducing the thermal and mechanical properties of the resulting polymer. [22] The pyrrolidone ring-based polyamides showed corrosive behavior in soil and photo-induced solubilization under UV light, which induce hydrolytic ring-opening. [21,23,24] In particular, symmetrical bis(pyrrolidone)-based dicarboxylic acids prepared from itaconic acid are polymerized and yield amorphous and degradable polymers with low T g values that are susceptible to enzymatic depolymerization. [25,26] However, conventional nonchiral polyamides such as nylon 6, nylon 66, and nylon 11 are not degradable whereas polyamides (nylon 4 and its copolymer nylon-4,4 and -5,4), which were derived from γ-aminobutyric acid (GABA) are biodegradable. [27][28][29] The polyamides from symmetrical monomers were studied, but monomers having head-tail asymmetry such as amino acids should be effective on The use of renewable feedstock for polymers has led to poor thermomechanical properties with high production costs. Herein, the production of novel chiral dicarboxylic acids derived from renewable itaconic and amino acids (d-or l-leucine) is reported. In this study, rigid chiral heterocyclic dicarboxylic acid monomers are obtained with high purity from itaconic acid-derived dimethyl itaconate as a starting material. Chirally interactive polyamides are prepared via melt polycondensation of hexamethylenediamine with heterocycl...

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Section: Synthesis Of Chiral Diacidmentioning

confidence: 99%

Section: Synthesis Of Chiral Diacidmentioning

confidence: 99%

High‐Performance BioNylons from Itaconic and Amino Acids with Pepsin Degradability

Ali

Kaneko

2021

Advanced Sustainable Systems

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“…Aminobisphenolate complexes of main group elements (for example, Al [ 14 , 15 , 16 , 17 , 18 , 19 ], alkali metals [ 20 , 21 , 22 ], Ca [ 21 ], Mg [ 23 ]), transition metals (for example, Ti [ 19 ]) and lanthanides [ 24 , 25 ] have been reported to catalyze ROP reactions, but by now there is absolutely no information not only about catalysis but also about the synthesis of such gallium complexes in general. At the same time, gallium is a non-toxic metal if one may consider the concentrations of metal compounds that remain in the polymer during its synthesis [ 26 ], in addition, there are examples of the use of some gallium complexes in medicine [ 27 ], and gallium complexes of various structures (for example, diamido-ether dianionic ligands, (aminomethyl)phenolate monoanionic ligands, 8-quinolinolato monoanionic ligands, salan dianionic ligands, salen dianionic ligands, bis(imino)phenoxide monoanionic ligands) are active in ROP as initiators, [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 ] thus aminobisphenolate gallium derivatives should be considered as potentially promising ROP initiators and interesting targets for their synthesis and investigation of their behavior in ROP.…”

Section: Introductionmentioning

confidence: 99%

Gallium (III) Complexes Based on Aminobisphenolate Ligands: Extremely High Active ROP-Initiators from Well-Known and Easily Accessible Compounds

Mankaev

Hasanova

Churakov³

et al. 2022

IJMS

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We report herein the synthesis and full characterizations of the first examples of gallium complexes based on “privileged” aminobisphenolate ligands which are easily available. These complexes turned out to be extremely active in the ring-opening polymerization of ε-caprolactone even at room temperature and highly active in the ROP of L-lactide. The combination of factors such as the easy availability of these compounds and the supposedly low toxicity, together with the extremely high activity in ROP, allows us to consider these compounds as suitable for use on an industrial scale for the synthesis of biodegradable polymers for biomedical applications.

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Dinuclear catalysts for the ring opening polymerization of lactide

Kremer

Mehrkhodavandi

2019

Coordination Chemistry Reviews

121

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Dialkylgallium alkoxides – a tool for facile and stereoselective synthesis of PLA–drug conjugates

Abstract: Pr (3)) in the ROP of rac-LA, where HOCHRCH 2 NHR' mimics the main skeleton of b-blockers 16 (Scheme 2). For 1-3, which were isolated as colourless crystals, the X-ray analysis revealed the presence of dimers in the solid state (Fig.

Cited by 4 publications

References 26 publications

High‐Performance BioNylons from Itaconic and Amino Acids with Pepsin Degradability

High‐Performance BioNylons from Itaconic and Amino Acids with Pepsin Degradability

Gallium (III) Complexes Based on Aminobisphenolate Ligands: Extremely High Active ROP-Initiators from Well-Known and Easily Accessible Compounds

Dinuclear catalysts for the ring opening polymerization of lactide

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