Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation

Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH4 at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (Td5% up to 170 °C) and low glass transition temperatures (as low as −42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme.

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Proton-conducting membranes based on side-chain-type sulfonated poly(ether ketone/ether benzimidazole)s via one-pot condensation

Journal of Membrane Science ◽

10.1016/j.memsci.2014.04.019 ◽

2014 ◽

Vol 465 ◽

pp. 100-106 ◽

Cited By ~ 17

Author(s):

Mengbing Cui ◽

Zhenghui Zhang ◽

Ting Yuan ◽

Hui Yang ◽

Liang Wu ◽

...

Keyword(s):

Side Chain ◽

One Pot ◽

Proton Conducting ◽

One Pot Condensation ◽

Ether Ketone ◽

Conducting Membranes ◽

Chain Type ◽

Sulfonated Poly

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Reaction of allyl iminophosphoranes with ketenes and acyl chlorides: one-pot preparation of 4-pentenenitriles

Tetrahedron ◽

10.1016/s0040-4020(01)81880-9 ◽

1993 ◽

Vol 49 (23) ◽

pp. 5153-5168 ◽

Cited By ~ 17

Author(s):

Pedro Molina ◽

Mateo Alajarín ◽

Carmen López-Leonardo ◽

Julian Alcántara

Keyword(s):

One Pot ◽

Acyl Chlorides

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Organometallics in prostaglandin synthesis

Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences ◽

10.1098/rsta.1988.0109 ◽

1988 ◽

Vol 326 (1592) ◽

pp. 579-585 ◽

Cited By ~ 2

Keyword(s):

Conjugate Addition ◽

Prostaglandin Synthesis ◽

Side Chain ◽

Prostaglandin E ◽

Controlled Synthesis ◽

One Pot ◽

Naturally Occurring ◽

Chain Unit ◽

Alkyl Iodides

An extremely short way to prostaglandins has been opened by combining the newly devised organometallic methodologies. Convergent, one-pot creation of the prostanoid framework is achieved by organocopper conjugate addition of the S-configurated ω-side-chain unit to (R)-4-trialkylsiloxy-2-cyclopentenone followed by the organotin-aided trapping of the enolate intermediate by α-side-chain alkyl iodides. Prostaglandin E 2 can be prepared in only three steps from the chiral building units. The protected 5,6-didehydro-PGE 2 derivatives thus obtained serve as common intermediates for the synthesis of a variety of naturally occurring prostaglandins including prostacyclin. This approach is also useful for the controlled synthesis of isocarbacyclin.

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Synthesis of β-arylated alkylamides via Pd-catalyzed one-pot installation of a directing group and C(sp3)–H arylation

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.12.108 ◽

2016 ◽

Vol 12 ◽

pp. 1122-1126 ◽

Cited By ~ 11

Author(s):

Yunyun Liu ◽

Yi Zhang ◽

Xiaoji Cao ◽

Jie-Ping Wan

Keyword(s):

One Pot ◽

Acyl Chlorides ◽

Aryl Iodides ◽

Directing Group

The synthesis of β-arylated alkylamides via alkyl C–H bond arylation has been realized by means of direct one-pot reactions of acyl chlorides, aryl iodides and 8-aminoquinoline. Depending on the structure of the starting materials, both single and double β-arylated alkylamides could be accessed.

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Pyrrole-Mediated Peptide Cyclization Identified through Genetically Reprogrammed Peptide Synthesis

Biomedicines ◽

10.3390/biomedicines6040099 ◽

2018 ◽

Vol 6 (4) ◽

pp. 99 ◽

Cited By ~ 2

Author(s):

Klaas Decoene ◽

Willem Vannecke ◽

Toby Passioura ◽

Hiroaki Suga ◽

Annemieke Madder

Keyword(s):

Peptide Synthesis ◽

Cyclic Peptide ◽

Solid Phase ◽

Solid Phase Peptide Synthesis ◽

Screening Method ◽

In Vitro Translation ◽

Side Chain ◽

One Pot ◽

Depth Analysis

Flexible in vitro translation (FIT) was used as a screening method to uncover a new methodology for peptide constraining based on the attack of a nucleophilic side-chain functionality onto an oxidized furylalanine side chain. A set of template peptides, each containing furylalanine as furan-modified amino acid and a nucleophilic residue (Cys, His, Lys, Arg, Ser, or Tyr), was produced through FIT. The translation mixtures were treated with N-bromosuccinimide (NBS) to achieve selective furan oxidation and subsequent MALDI analysis demonstrated Lys and Ser as promising residues for cyclisation. Solid-phase peptide synthesis (SPPS) was used to synthesize suitable amounts of material for further in-depth analysis and characterisation. It was found that in the case of the peptide containing lysine next to a furylalanine residue, a one-pot oxidation and reduction reaction leads to the generation of a cyclic peptide featuring a pyrrole moiety as cyclisation motif, resulting from the attack of the lysine side chain onto the oxidized furylalanine side chain. Structural evidence was provided via NMR and the generality of the methodology was explored. We hereby expand the scope of our previously developed furan-based peptide labeling and crosslinking strategy.

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Three-component synthesis of highly functionalized aziridines containing a peptide side chain and their one-step transformation into β-functionalized α-ketoamides

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.12.166 ◽

2016 ◽

Vol 12 ◽

pp. 1772-1777 ◽

Cited By ~ 3

Author(s):

Lena Huck ◽

Juan F González ◽

Elena de la Cuesta ◽

J Carlos Menéndez

Keyword(s):

Single Step ◽

Side Chain ◽

One Pot ◽

Aziridine Ring ◽

Component Process ◽

Mild Conditions ◽

One Step

A sequential three-component process is described, starting from 3-arylmethylene-2,5-piperazinediones and involving a one-pot sequence of reactions achieving regioselective opening of the 2,5-diketopiperazine ring and diastereoselective generation of an aziridine ring. This method allows the preparation of N-unprotected, trisubstituted aziridines bearing a peptide side chain under mild conditions. Their transformation into β-trifluoroacetamido-α-ketoamide and α,β-diketoamide frameworks was also achieved in a single step.

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A Synthesis of 4-Chloro-2-(trichloromethyl)pyrimidines and Their Study in Nucleophilic Substitution

Synthesis ◽

10.1055/s-0037-1610270 ◽

2018 ◽

Vol 51 (02) ◽

pp. 530-537 ◽

Cited By ~ 1

Author(s):

Moisés Romero-Ortega ◽

Michelle Trujillo-Lagunas ◽

Ignacio Medina-Mercado ◽

Ivann Zaragoza-Galicia ◽

Horacio Olivo

Keyword(s):

Nucleophilic Substitution ◽

Intramolecular Cyclization ◽

Nitrogen Heterocycles ◽

Cyclization Reaction ◽

Substitution Reactions ◽

Pyrimidine Derivatives ◽

One Pot ◽

Acyl Chlorides ◽

Nucleophilic Substitution Reactions ◽

One Pot Synthesis

A convenient two-step, one-pot synthesis of 4-chloro-2-(trichloromethyl)pyrimidines starting from 2-(trichloromethyl)-1,3-diazabutadienes is described. These nitrogen heterocycles were prepared by a sequential acylation/intramolecular cyclization reaction between 2-(trichloromethyl)-1,3-diazabutadienes and acyl chlorides in the presence of triethylamine followed by treatment with POCl3. This is the first report for the synthesis of this type of 4-chloro-2-(trichloromethyl)pyrimidine derivatives and serves as a source for a wide variety of other substituted pyrimidines by nucleophilic substitution reactions.

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Influence of Calcium Binding on Conformations and Motions of Anionic Polyamino Acids. Effect of Side Chain Length

Polymers ◽

10.3390/polym12061279 ◽

2020 ◽

Vol 12 (6) ◽

pp. 1279

Author(s):

Dmitry Tolmachev ◽

Natalia Lukasheva ◽

George Mamistvalov ◽

Mikko Karttunen

Keyword(s):

Amino Acids ◽

Chain Length ◽

Calcium Binding ◽

Md Simulations ◽

Side Chain ◽

Replica Exchange ◽

Side Chain Length ◽

Hamiltonian Replica Exchange ◽

Cacl2 Concentration ◽

Chain Lengths

Investigation of the effect of CaCl2 salt on conformations of two anionic poly(amino acids) with different side chain lengths, poly-(α-l glutamic acid) (PGA) and poly-(α-l aspartic acid) (PASA), was performed by atomistic molecular dynamics (MD) simulations. The simulations were performed using both unbiased MD and the Hamiltonian replica exchange (HRE) method. The results show that at low CaCl2 concentration adsorption of Ca2+ ions lead to a significant chain size reduction for both PGA and PASA. With the increase in concentration, the chains sizes partially recover due to electrostatic repulsion between the adsorbed Ca2+ ions. Here, the side chain length becomes important. Due to the longer side chain and its ability to distance the charged groups with adsorbed ions from both each other and the backbone, PGA remains longer in the collapsed state as the CaCl2 concentration is increased. The analysis of the distribution of the mineral ions suggests that both poly(amino acids) should induce the formation of mineral with the same structure of the crystal cell.

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