Synthesis and Structural Studies of 2,3-Disubstituted Poly(β-peptide)s

Garcı́a-Martı́n, Marı́a de Gracia; de-Paz, M.-Violante; García-Alvarez, Monserrat; Muñoz‐Guerra, Sebastián; Galbis, Juan A.

doi:10.1021/ma0022248

Cited by 8 publications

(6 citation statements)

References 12 publications

(20 reference statements)

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“…Chiral polyamides 3 were also prepared by ROP of the β-lactam of 3-amino-3-deoxy-2,4,5,6-tetra-Omethyl-D-altronic acid 115,116 and from isopropylidene-D-glyceraldehyde (Scheme 20). 117,118 An enantiopure chiral β-polyamido-saccharide (88) was synthesized by Grinstaff et al 119 by an anionic ROP of the bicyclic β-lactam monomer 86 synthesized in one step from benzyl-protected D-glucal (Scheme 21). 120 Circular dichroism experiments suggest that the deprotected polymer (89) possesses a regular secondary structure in aqueous solution, which agrees favorably with the prediction of a helical structure using molecular modeling.…”

Section: Ab-type Polyamidesmentioning

confidence: 99%

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Synthetic Polymers from Sugar-Based Monomers

et al. 2015

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Scheme 2. (a) Lactide Polymerization Coinitiated by Carbohydrates; (b) Copolymerization of Lactone Derived from D-Gluconolactone and ε-Caprolactone (CL) Scheme 3. Polyesters Based on Pentitols and Pentaric Acid Scheme 4. Protein-Resistant Polyesters Based on Galactitol and D-Mannitol Scheme 5. Polyesters Based on L-Tartaric Acid Derivatives Scheme 6. PBS Copolyesters Based on L-Tartaric Acid Derivatives Scheme 7. Erythritol-Based Polyesters Containing Triazol Rings

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Section: Ab-type Polyamidesmentioning

confidence: 99%

“…Chiral polyamides 3 were also prepared by ROP of the β-lactam of 3-amino-3-deoxy-2,4,5,6-tetra- O -methyl- d -altronic acid , and from isopropylidene- d -glyceraldehyde (Scheme ). , …”

Section: Polyamidesmentioning

confidence: 99%

Synthetic Polymers from Sugar-Based Monomers

et al. 2015

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“…β-polypeptides are a class of synthetic polymers known to form defined secondary structures and are of significant interest for a variety of applications. 20 Based on molecular modeling, α-N-1,2- d -glc PASs are predicted to have a helical structure that is promoted by extensive internal hydrogen-bonding and by the rigidity of the pyranose-polyamide backbone (Figure 1). …”

Section: Introductionmentioning

confidence: 99%

Poly-amido-saccharides: Synthesis via Anionic Polymerization of a β-Lactam Sugar Monomer

2012

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Chiral poly-amido-saccharides (PASs) with a defined molecular weight and narrow polydispersity are synthesized using an anionic ring-opening polymerization of a β-lactam sugar monomer. The PASs have a previously unreported main chain structure that is composed of pyranose rings linked through the 1- and 2-positions by an amide bond with α-stereochemistry. The monomer is synthesized in one-step from benzyl-protected d-glucal and polymerized using mild reaction conditions to give degrees of polymerization ranging from 25 to >150 in high yield. Computational modeling reveals how the monomer’s structure and steric bulk affect the thermodynamics and kinetics of polymerization. Protected and deprotected polymers and model compounds are characterized using a variety of methods (NMR, GPC, IR, DLS, etc.). Reductive debenzylation provides the deprotected, hydrophilic polymers in high yield. Based on circular dichroism, the deprotected polymers possess a regular secondary structure in aqueous solution, which agrees favorably with the prediction of a helical structure using molecular modeling. Furthermore, we provide evidence suggesting that the polymers bind the lectin concanavalin A at the same site as natural carbohydrates, showing the potential of these polymers to mimic natural polysaccharides. PASs offer the advantages associated with synthetic polymers, such as greater control over structure and derivitization, and less batch-to-batch variation. At the same time, they preserve many of the structural features of natural polysaccharides, such as a stereochemically regular, rigid pyranose backbone, that make natural carbohydrate polymers important materials both for their unique properties and useful applications.

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“…In contrast, the pseudohalogenic character of aliphatic azides is less well-known. Although azides have been reported to undergo elimination to form alkenes, to our knowledge no nucleophilic substitution has ever been reported of an azido group in an aliphatic chain. Herein, we describe the unexpected reactivity of 3-azidopropionic acid with standard coupling reagents such as carbodiimides, opening access to a variety of aza heterocyclic systems under mild conditions.…”

Section: Introductionmentioning

confidence: 91%