Synthesis of ferrocene-functionalized monomers for biodegradable polymer formation

Upton, Brianna M.; Gipson, Raymond M.; Duhović, Selma; Lydon, Brian R.; Matsumoto, Nicholas M.; Maynard, Heather D.; Diaconescu, Paula L.

doi:10.1039/c3qi00041a

Cited by 20 publications

(20 citation statements)

References 55 publications

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“…Diaconescu and coworkers reported a series of three different a-ferrocenyl-d-valerolactones (A24-A26) and six ferrocenylsubstituted trimethylene carbonate (TMC) monomers (C5-C10), all obtained by click chemistry of azide-functionalized ferrocene to A22, 5-(propynyl)-1,3-dioxane-2-one and propargyl 5-methyl-2oxo-1,3-dioxane-5-carboxylate (C11) (see also below). 87 While all TMC monomers were polymerizable with DBU/TU as the catalyst (1,8-diazabicycloundec-7-ene and 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexyl thiourea), A24-A26 were not able to be polymerized neither as homo-nor copolymers.…”

Section: Polyestersmentioning

confidence: 98%

“…Hydroxyethyl methacrylate (HEMA) was grafted from copolymers as macroinitiator, and the amphiphilic polymers self-assembled in micelles. Diaconescu and coworkers 87 reported several ferrocenecontaining TMCs (5-substituted (C5-C7) and 5-methyl-5 0substituted (C8-C10)), polymerized them and studied their redox potential for biological studies. Proceeding from 2-(prop-2-yn-1yl)-propane-1,3-diol, cyclization was achieved with triphosgene.…”

Section: C54mentioning

confidence: 99%

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Functional biodegradable polymers via ring-opening polymerization of monomers without protective groups

2018

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Biodegradable polymers are of current interest and chemical functionality in such materials is often demanded in advanced biomedical applications. Functional groups often are not tolerated in the polymerization process of ring-opening polymerization (ROP) and therefore protective groups need to be applied. Advantageously, several orthogonally reactive functions are available, which do not demand protection during ROP. We give an insight into available, orthogonally reactive cyclic monomers and the corresponding functional synthetic and biodegradable polymers, obtained from ROP. Functionalities in the monomer are reviewed, which are tolerated by ROP without further protection and allow further post-modification of the corresponding chemically functional polymers after polymerization. Synthetic concepts to these monomers are summarized in detail, preferably using precursor molecules. Post-modification strategies for the reported functionalities are presented and selected applications highlighted.

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Section: Polyestersmentioning

confidence: 98%

Section: C54mentioning

confidence: 99%

Functional biodegradable polymers via ring-opening polymerization of monomers without protective groups

2018

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“…However, in the case of the reduced species, a direct zinc-phosphine interaction was not observed. Despite this finding, and because of our interest in redox-switchable catalytic processes ( Abubekerov et al., 2016 , Abubekerov et al., 2017 , Wang et al., 2014 , Wang et al., 2015 , Quan and Diaconescu, 2015 , Brosmer and Diaconescu, 2015 , Abubekerov and Diaconescu, 2015 , Upton et al., 2014 , Broderick et al., 2011a , Broderick et al., 2011b , Broderick et al., 2011c , Quan et al., 2016 , Quan et al., 2017 , Lowe et al., 2017 , Shepard and Diaconescu, 2016 ), we set out to investigate the influence of the redox state of fc P,B on the zinc-mediated ring-opening polymerization of cyclic esters and carbonates. In addition, an investigation into the redox and polymerization activity of a monomeric ferrocene-chelating heteroscorpionate zinc complex, (fc P,B )Zn(OPh), is reported.…”

Section: Introductionmentioning

confidence: 99%

Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II) Complexes

et al. 2018

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SummaryNeutral zinc alkoxide complexes show high activity toward the ring-opening polymerization of cyclic esters and carbonates, to generate biodegradable plastics applicable in several areas. Herein, we use a ferrocene-chelating heteroscorpionate complex in redox-switchable polymerization reactions, and we show that it is a moderately active catalyst for the ring-opening polymerization of L-lactide, ɛ-caprolactone, trimethylene carbonate, and δ-valerolactone. Uniquely for this type of catalyst, the oxidized complex has a similar polymerization activity as the corresponding reduced compound, but displays significantly different rates of reaction in the case of trimethylene carbonate and δ-valerolactone. Investigations of the oxidized compound suggest the presence of an organic radical rather than an Fe(III) complex. Electronic structure and density functional theory (DFT) calculations were performed to support the proposed electronic states of the catalytic complex and to help explain the observed reactivity differences. The catalyst was also compared with a monomeric phenoxide complex to show the influence of the phosphine-zinc interaction on catalytic properties.

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“…Nucleophilic substitution reaction of 4‐(bromoethoxy) quinolines 6a–d with NaN 3 led to azido quinoline derivatives 11a–d . The targeted ferrocenyl and quinoline, and quinolone conjugates 7a–7b, 8a–8b , 9a , 9b , 10a and 10b were synthesized via copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) reaction of 1‐methylazidoferrocene and 1‐azidoethylferrocene, prepared from corresponding hydroxyl derivatives, and O ‐ or N ‐alkylated 4‐quinolones ( 4a–d , 5a and 5b ). Moreover, reaction of 6‐substituted 4‐(2‐azidoethoxy)‐2‐(trifluoromethyl) quinoline derivatives 11a–d with ethynylferrocene afforded quinoline and ferrocene hybrids connected through the 1,4‐disubstituted 1,2,3‐triazole derivatives 12a–d .…”

Section: Resultsmentioning

confidence: 99%

“…Compounds 2‐(trifluoromethyl)quinolin‐4(1 H )‐one ( 3a ), 6‐methyl‐2‐(trifluoromethyl)‐quinolin‐4(1 H )‐one ( 3b ), 6‐phenyl‐2‐(trifluoromethyl)quinolin‐4(1 H )‐one ( 3d ), 1‐methylazidoferrocene and 1‐azidoethylferrocene were synthesized according to known procedure.…”

Section: Methodsmentioning

confidence: 99%

Quinoline and ferrocene conjugates: Synthesis, computational study and biological evaluations

Maračić

Lapić

Djaković

et al. 2018

Applied Organom Chemis

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Novel O-alkylated quinoline and N-alkylated 4-quinolone derivatives attached to the ferrocene moiety through 4,1-(7a-d, 8a-d and 12a-d) and 1,4-disubstituted (9a, 9b, 10a and 10b) 1,2,3-triazole moiety were synthesized. The observed regioselectivity of O-vs. N-alkylation was explored by the use of NMR and computational techniques. Among the N-alkylated derivatives, the quinolone-ferrocene conjugate 9a displayed marked activities against chronic myeloid leukemia in blast crisis (K562) and Burkitt lymphoma (Raji). The 6-chloroquinolone-ferrocene conjugate 12c, with selective inhibitory activity on Raji cells and no cytostatic effect on normal MDCK1 cells was highlighted as the most promising anticancer organometallic complex in a group of O-alkylated quinolines.

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Synthesis of ferrocene-functionalized monomers for biodegradable polymer formation

Cited by 20 publications

References 55 publications

Functional biodegradable polymers via ring-opening polymerization of monomers without protective groups

Functional biodegradable polymers via ring-opening polymerization of monomers without protective groups

Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II) Complexes

Quinoline and ferrocene conjugates: Synthesis, computational study and biological evaluations

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