Vinylation and the Formation of Acylals

Hurd, Charles D.; Roach, Robert C.; Huffman, C. W.

doi:10.1021/ja01582a031

Cited by 11 publications

(8 citation statements)

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“…Surprisingly, up to date, there are only a few publications that deal with photopolymerization of VEs 6–9. Sensitivity of classical VE synthetic routes toward functional groups10 along with the need for expensive catalysts11 may explain why there are currently only a limited number of monofunctional and just one difunctional VE commercially available. Recently, BASF filed an interesting patent, which included a new reaction pathway toward VEs on an industrial scale using cheap reagents (alkynes and carboxylic acids) 12,13.…”

Section: Introductionmentioning

confidence: 99%

Thiol‐ene photopolymerization for efficient curing of vinyl esters

Mautner

Qin

Wutzel

et al. 2012

J. Polym. Sci. A Polym. Chem.

102

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Monomers for radical photopolymerization based on vinyl esters (VEs) have recently been identified as suitable alternatives to (meth)acrylates on account of their low irritancy and cytotoxicity. The drawback of most VEs with abstractable hydrogens is their relatively low reactivity compared with (meth)acrylates. Within this article, we proved by photo-differential scanning calorimetry measurements and real-time Fourier transform infrared spectroscopy that the thiol-ene concept is able to improve the photoreactivity of these VEs to a large extent to a level between those of acrylates and methacrylates.Other VEs have now a reactivity of at least the level of similar acrylates. Mechanical properties as determined by Dynamic Mechanical Analysis and Charpy impact tests showed significant toughening of these materials. Furthermore, we were able to confirm low toxicity of all components by osteoblast cell culture experiments.

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Section: Introductionmentioning

confidence: 99%

Thiol‐ene photopolymerization for efficient curing of vinyl esters

Mautner

Qin

Wutzel

et al. 2012

J. Polym. Sci. A Polym. Chem.

102

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“…Compared to acrylates and methacrylates, only a few vinyl esters are commercially available. The reason might be that the common synthetic route to vinyl esters using mercury(II)acetate as a catalyst is very sensitive towards functional groups limiting the monomer design 20. Alternative methods use Pd(II) salts as catalyst21, 22 or selenium based precursors 23.…”

Section: Introductionmentioning

confidence: 99%

Vinyl esters: Low cytotoxicity monomers for the fabrication of biocompatible 3D scaffolds by lithography based additive manufacturing

Heller

Schwentenwein

Russmueller

et al. 2009

J. Polym. Sci. A Polym. Chem.

143

142

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Lithography based additive manufacturing technologies (AMT) like stereolithography or digital light processing have become appealing methods for the fabrication of 3D cellular scaffolds for tissue engineering and regenerative medicine. To circumvent the use of (meth)acrylate-based photopolymers, that suffer from skin irritation and sometimes cytotoxicity, new monomers based on vinyl esters were prepared. In vitro cytotoxicity studies with osteoblast-like cells proofed that monomers based on vinyl esters are significantly less cytotoxic than (meth)acrylates. Photoreactivity was followed by photo-differential scanning calorimetry and the mechanical properties of the photocured materials were screened by nanoindentation. Conversion rates and indentation moduli between those of acrylate and methacrylate references could be observed. Furthermore, osteoblast-like cells were successfully seeded onto polymer specimens. Finally, we were able to print a 3D test structure out of a vinyl ester-based formulation by l-SLA with a layer thickness of 50 lm. For in vivo testing of vinyl esters these 3D scaffolds were implanted into surgical defects of the distal femoral bone of adult New Zealand white rabbits. The obtained histological results approved the excellent biocompatibility of vinyl esters. V V C 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6941-6954, 2009

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“…The solution was adjusted to pH 1 (1m HCl) and the solvents were removed in vacuo to give a crude solid, which was purified by flash column chromatography (CH 2 4-Hydrogen-1-prop-2-enyl-butane dicarboxylate (12): A mixture of succinic anhydride (5 g, 50 mmol) and allyl alcohol (3 mL, 50 mmol) were refluxed for 3 h. The mixture was then distilled at reduced pressure to afford monoester 12 as a colorless liquid (5 g, 72 %), bp 128 8C (4 mm of Hg) [ref. [14] Acid chloride (13): Oxalyl chloride (4.2 mL, 47.5 mmol) was added to a stirred solution of monoester 12 (5 g, 31.7 mmol) in CH 2 Cl 2 (20 mL). Two drops of DMF were added and the mixture stirred for two hours under nitrogen.…”

Section: Methodsmentioning

confidence: 99%

“…The peptidic fragment was prepared, as the allyl ester 14 (Scheme 2), by reaction of succinic anhydride with allyl alcohol, followed by conversion of monoacid 12 [14] to the acid chloride 13, which, in turn, was used to acylate phenylalanine. A PyBOP-(PyBOP benzotriazol-1-yloxy-tripyrrolidinophosphonium hexafluorophosphate [15] or DCC-mediated coupling of acid 14 to 2,6-diaminopyridine gave the desired monoacylated product 15, but with complete racemisation of the phenylalanine derived chiral centre, presumably via an oxazolone intermediate.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Binding Properties of a Macrocyclic Peptide Receptor

et al. 1999

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Macrocyclic receptor 1 has been synthesised, as a racemate and as a single enantiomer, utilising a Stille coupling for the formation of the biphenyl portion and a macrolactamisation as the final step. The binding properties for the racemic and the homochiral macrocycle with amino acid and dipeptide derivatives, in CDCl 3 solution, have been investigated. In the case of racemic 1, addition of homochiral peptide substrates led to two distinct diastereomeric complexes, and the well separated signals for several protons in the 1 H NMR spectrum could be conveniently followed in titration experiments, allowing determination of both binding constants for the two diastereoisomeric complexes, and indicating that 1 is capable of enantioselective recognition. Titration of homochiral 1 with the same peptide substrates allowed the sense of the enantioselectivity to be determined, and experiments with a greater range of substrates indicated that 1 is particularly effective for the recognition of N-Cbz-balanyl-l-amino acids, the strongest binding being observed with N-Cbz-b-alanyll-alanine (À DG ass 19.9 kJ mol À1). Notably the binding of N-Cbz-b-alanyl-llactic acid was considerably weaker (À DG ass 13.1 kJ mol À1 ), presumably due to replacement of an NH hydrogen-bond donor in the case of N-Cbz-balanyl-l-alanine with an oxygen lonepair in the case of N-Cbz-b-alanyl-llactic acid. Molecular modelling and 2 D NMR studies on the free macrocycle 1 and associated complexes did not provide conclusive evidence for the structure of the host ± guest complexes, but did serve to emphasise the flexibility of 1, which despite this flexibility, shows strong, selective binding of certain peptide guests.

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Vinylation and the Formation of Acylals

Cited by 11 publications

References 0 publications

Thiol‐ene photopolymerization for efficient curing of vinyl esters

Thiol‐ene photopolymerization for efficient curing of vinyl esters

Vinyl esters: Low cytotoxicity monomers for the fabrication of biocompatible 3D scaffolds by lithography based additive manufacturing

Synthesis and Binding Properties of a Macrocyclic Peptide Receptor

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