Nucleophilic Ring‐Opening of Azetidinium Ions: Insights into Regioselectivity

Couty, François; David, Olivier; Durrat, François; Evano, Gwilherm; Lakhdar, Sami; Marrot, Jérôme; Vargas-Sanchez, Monica

doi:10.1002/ejoc.200600200

Cited by 54 publications

(27 citation statements)

References 33 publications

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“…Azetidinium ion ring opening with nucleophiles such as halides, alkoxides, phenoxides, amines and cyanide is reported to be facile (35–37). Nucleophilic reaction of azetidinium ring of 6 with mono-Boc-1,3-propanediamine (38,39) in dichloromethane under reflux resulted in intermediate 7 in 90% yield, with about 5% of 8 separated chromatographically.…”

Section: Resultsmentioning

confidence: 99%

Bisethylnorspermine Lipopolyamine as Potential Delivery Vector for Combination Drug/Gene Anticancer Therapies

Dong

et al. 2010

Pharm Res

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Purpose To design novel synthetic gene delivery system in which the carrier molecule functions dually as a carrier and a cytotoxic agent targeting dysregulated polyamine metabolism in cancer. Methods Bisethylnorspermine (BENSpm) lipopolyamine was synthesized and its toxicity evaluated by MTS assay in MCF-7 and MCF-10A cells. Transfection activity was determined using luciferase plasmid DNA. Results Asymmetrical lipid analogue of polyamine anticancer drug BENSpm was synthesized using nucleophilic ring opening of azetidinium ion. The synthesized LipoBENSpm showed cytotoxicity comparable to that of parent BENSpm in human breast cancer cell line MCF-7 but mediated 3–4 orders magnitude higher transfection activity. Importantly, cytostatic activity of BENSpm, typically in a low µM range, falls within a relevant and typical concentration range required for efficient gene delivery. Conclusions These findings make gene delivery vectors based on BENSpm promising candidates for combination drug/gene approaches to the treatment of cancer.

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Section: Resultsmentioning

confidence: 99%

Bisethylnorspermine Lipopolyamine as Potential Delivery Vector for Combination Drug/Gene Anticancer Therapies

Dong

et al. 2010

Pharm Res

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“…Due to the straightforwardness of this synthetic scheme, which leads to enantiomerically pure functionalized azetidines of high synthetic potential, 10 it was highly desirable to generalize this sequence when R is an alkyl group. However, in this case, the chlorination step leads to regioisomeric chlorides 6 and 9, due to a low selectivity during the opening of the intermediate aziridinium ion by the chloride anion (Scheme 2).…”

Section: Methodsmentioning

confidence: 99%

A straightforward synthesis of 3-substituted azetidinic amino acids

Sivaprakasham¹,

Couty²,

Evano³

et al. 2006

Arkivoc

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A series of enantiomerically pure N,N-disubstituted β-amino alcohols were chlorinated by treatment with thionyl chloride. This reaction afforded a mixture of regioisomeric β-amino chlorides that could be equilibrated to the more stable regioisomer by heating in DMF. The secondary chlorides thus obtained were engaged in an intramolecular anionic ring-closure to give access to fully protected enantio-and diastereoisomerically pure 2,3-cis-disubstituted azetidinic amino acid. One of the latter was deprotected for inclusion in a tripeptide sequence. This synthetic methodology was applied for N,N-disubstituted γ-amino alcohols, leading to 3-or 5-substituted proline derivatives but with a low 2,3-or 2,5-diastereoselectivity.

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“…Reagents that react with the sulfate groups of polysaccharides are less explored; however, they may be useful and may have an impact in biological, medicinal, and material applications. From previous research, it is known that azetidinium salts react preferentially with carboxylates, amines, phenols, and phosphorus nucleophiles . Azetidinium salts are positively charged, which to some extent governs their adsorption to carboxylic acids via electrostatic interaction.…”

Section: Introductionmentioning

confidence: 99%

Increased thermal stability of nanocellulose composites by functionalization of the sulfate groups on cellulose nanocrystals with azetidinium ions

Börjesson

Sahlin

Bernin

et al. 2017

J of Applied Polymer Sci

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Cellulose nanocrystals (CNCs) prepared via sulfuric acid hydrolysis are decorated with sulfate groups that yield a stable water suspension. To make the CNCs adaptable for use in composites, the hydroxyl groups on the surface are usually hydrophobized. In this article, an alternative hydrophobization method is described in which the sulfate groups are conjugated with azetidinium salts. The results of this study show that the sulfate groups can be functionalized with azetidinium salts and from thermal studies, it was discovered that the functionalization led to a 100 8C increase in thermal stability, compared with unmodified CNCs. The nanocomposites prepared by extrusion of CNC-coated low-density polyethylene powder displayed similar mechanical properties as the CNC-reference sample, but without the discoloration, due to the increased thermal stability. In conclusion, the azetidinium reagent reacts preferentially with sulfate groups, and this new type of chemical conversion of sulfate groups on polysaccharides will be beneficial in nanocomposite manufacturing.

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Nucleophilic Ring‐Opening of Azetidinium Ions: Insights into Regioselectivity

Cited by 54 publications

References 33 publications

Bisethylnorspermine Lipopolyamine as Potential Delivery Vector for Combination Drug/Gene Anticancer Therapies

Bisethylnorspermine Lipopolyamine as Potential Delivery Vector for Combination Drug/Gene Anticancer Therapies

A straightforward synthesis of 3-substituted azetidinic amino acids

Increased thermal stability of nanocellulose composites by functionalization of the sulfate groups on cellulose nanocrystals with azetidinium ions

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