- A general approach to substituted itaconate esters
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A general approach to the synthesis of various itaconates including 3-substituted esters is presented. The complementarity of the approach is also shown.
- Dowd,Wilk
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Read Online
- ItaCORMs: conjugation with a CO-releasing unit greatly enhances the anti-inflammatory activity of itaconates
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Endogenous itaconate as well as the gasotransmitter CO have recently been described as powerful anti-inflammatory and immunomodulating agents. However, each of the two agents comes along with a major drawback: Whereas itaconates only exert beneficial effects at high concentrations above 100 μM, the uncontrolled application of CO has strong toxic effects. To solve these problems, we designed hybrid prodrugs,i.e.itaconates that are conjugated with an esterase-triggered CO-releasing acyloxycyclohexadiene-Fe(CO)3unit (ItaCORMs). Here, we describe the synthesis of differentItaCORMsand demonstrate their anti-inflammatory potency in cellular assays of primary murine immune cells in the low μmolar range (a promising new class of hybrid compounds with high clinical potential as anti-inflammatory agents.
- Bauer, Britta,Krause, Bernhard M.,Neud?rfl, J?rg-Martin,Schmalz, Hans-Günther,Wieder, Thomas
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supporting information
p. 2053 - 2059
(2022/01/25)
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- Synthesis and Bioactivity of Polymer-Based Synthetic Mimics of Antimicrobial Peptides (SMAMPs) Made from Asymmetrically Disubstituted Itaconates
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A series of asymmetrically disubstituted diitaconate monomers is presented. Starting from itaconic anhydride, functional groups could be placed selectively at the two nonequivalent carbonyl groups. By using 2D NMR spectroscopy, it was shown that the first functionalization step occurred at the carbonyl group in the β position to the double bond. These monomers were copolymerized with N,N-dimethylacrylamide (DMAA) to yield polymer-based synthetic mimics of antimicrobial peptides (SMAMPs). They were obtained by free radical polymerization, a metal-free process, and still maintained facial amphiphilicity at the repeat unit level. This eliminates the need for laborious metal removal and is advantageous from a regulatory and product safety perspective. The poly(diitaconate-co-DMAA) copolymers obtained were statistical to alternating, and the monomer feed ratio roughly matched that of the repeat unit content of the copolymers. Investigations of varied R group hydrophobicity, repeat unit ratio, and molecular mass on antimicrobial activity against Escherichia coli and on compatibility with human keratinocytes showed that the polymers with the longest R groups and lowest DMAA content were the most antimicrobial and hemolytic. This is in agreement with the biological activity of previously reported SMAMPs. Thus, the design concept of facial amphiphilicity has successfully been transferred, but the selectivity of these polymers for bacteria over mammalian cells still needs to be optimized.
- Boschert, David,Schneider-Chaabane, Alexandra,Himmelsbach, Andreas,Eickenscheidt, Alice,Lienkamp, Karen
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p. 8217 - 8227
(2018/05/30)
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- A novel and practical method for the synthesis of dinotefuran through Michael addition of nitromethane to diethyl maleate
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A novel and practical synthesis of dinotefuran 1, featuring a new access to it from known key intermediate (tetrahydrofuran-3-yl)-methanamine 5, has been achieved through Michael addition reaction of nitromethane to diethyl maleate in 6 steps with 45.5% total yield. This synthesis is scalable and hence has high potential for application to further synthetic elaboration on such new neonicotinoid insecticide dinotefuran 1.
- Li, Haifeng,Wang, Lailai
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p. 336 - 340
(2017/12/11)
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- Highly chemoselective esterification reactions and Boc/THP/TBDMS discriminating deprotections under samarium(III) catalysis
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The usefulness of SmCl3 as an excellent catalyst for chemoselective esterifications and selective removal of acid sensitive protecting groups such as Boc, THP, and TBDMS in the presence of one another is demonstrated through suitable examples.
- Gopinath, Pushparathinam,Nilaya, Surapaneni,Muraleedharan, Kannoth Manheri
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supporting information; experimental part
p. 1932 - 1935
(2011/06/21)
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- METHODS FOR THE SYNTHESIS OF OLEFINS AND DERIVATIVES
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The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.
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Page/Page column 44-47
(2009/05/29)
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- Versatile mesoporous carbonaceous materials for acid catalysis
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Starbon mesoporous materials were synthesized after pyrolysis of expanded starch and subsequently functionalised with sulfonated groups, providing highly active and reusable materials in various acid catalysed reactions. The Royal Society of Chemistry.
- Budarin, Vitaly L.,Clark, James H.,Luque, Rafael,Macquarrie, Duncan J.
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p. 634 - 636
(2007/10/03)
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- Preparation and Characterization of [5-13C]-(2S,4R)-Leucine and [4-13C]-(2S,3S)-Valine - Establishing Synthetic Schemes to Prepare Any Site-Directed Isotopomer of L-Leucine, L-Isoleucine and L-Valine
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In this paper a chemo-enzymatic method has been developed that gives access to any isotopomer of the essential amino acids isoleucine and valine. The method gives the correct introduction of the second chiral center in (2S,3S)-isoleucine and allows for discrimination between the two prochiral methyl groups in valine as shown by the preparation of (2S,3S)-[4- 13C] valine. For the preparation of (2S)-leucine in any isotopomeric form, the O'Donnell method to prepare optically active amino acids has been used. The protected glycine scaffold used in this method has been prepared by a strategy that allows access to any isotopomeric form. The preparation of [5-13C]-(2S,4R)-leucine shows that the O'Donnell method in combination with the Evans method to obtain chiral 2-methylpropyl iodide leads to a good discrimination between the two prochiral methyl groups. The O'Donnell strategy for the preparation of α-amino acids is preferred over other methods since the reaction conditions are mild, the chiral auxiliary can be easily recovered and the optically active product can be easily separated. For the preparation of isotopically enriched valine and isoleucine the O'Donnell method is not suitable, because the alkyl substituents involved have a secondary halide substituent which is sterically too hindered to give an effective reaction with the protected glycine. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Siebum, Arjan H. G.,Woo, Wei Sein,Lugtenburg, Johan
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p. 4664 - 4678
(2007/10/03)
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- Selective enzymatic transformations of itaconic acid derivatives: An access to potentially useful building blocks
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Hydrolytic enzymes regioselectively catalyze the hydrolysis of diethyl itaconate 5a to the monoester 5c and opening of itaconic anhydride 6 to the regioisomeric monoester 5b that was transformed into the hydroxy esters 2. This was used for the synthesis of β-methylene-γ-butyrolactone 7 and of the racemic epoxyalcohol 3, that was resolved by a highly enantioselective Pseudomonas fluorescens lipase-catalyzed transesterification into (S)-3 and (S)-8 (90 and 86% ee, respectively).
- Ferraboschi, Patrizia,Casati, Silvana,Grisenti, Paride,Santaniello, Enzo
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p. 3251 - 3258
(2007/10/02)
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- HIGH YIELD SYNTHESIS OF α PROPARGYLIC ACRYLIC ESTER : A GENERAL ACCESS TO α SUBSTITUTED ACRYLIC ESTERS
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A heterogeneous mediated, high yield, monopropargylation of ethyl benzoylacetate followed by a methylenation reaction using a formaldehyde addition-benzoyl elimination mechanism is described.This useful method is extended to the synthesis of α substituted acrylic esters.
- Queignec, Rene,Kirschleger, Bernard,Lambert, Francois,Aboutaj, Mohammed
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p. 1213 - 1224
(2007/10/02)
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