Glaser oxidative coupling on peptides: Stabilization of β-turn structure via a 1,3-butadiyne constraint

Auberger, Nicolas; Pisa, Margherita Di; Larregola, Maud; Chassaing, Gérard; Peroni, Elisa; Lavielle, Solange; Papini, Anna Maria; Lequin, Olivier; Mallet, Jean‐Maurice

doi:10.1016/j.bmc.2014.10.026

Cited by 12 publications

(17 citation statements)

References 37 publications

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“…Peptide sequences designed and synthesized in this study are reported in Table I. 19 Octapeptide sequences were also prepared (peptides 6, 11-13, respectively), taking into account the type I b-turn motif, not only in the core sequence, ERN(Glc)GHT, of CSF114(Glc), but also with a proline containing sequence, ERPN(Glc)HT, which has been shown to stabilize a type I b-turn. The collection of peptides was completed with the glucosylated hexapeptide containing the achiral residue N-propargylglycine (NPra) instead of L-Pra (peptide Ac-c[NPra-RN(Glc)GH-NPra]-NH 2 (5).…”

Section: Peptide Design and Synthesesmentioning

confidence: 99%

“…19 The linear unglucosylated Pra-containing peptide analog was shown to be very flexible, with a weak propensity for b-turn conformation around the central Asn-Gly sequence. These structures were compared to the unglucosylated analogs, which were previously characterized under similar conditions.…”

Section: Nmr Conformational Analysismentioning

confidence: 99%

“…Side chain-toside chain peptide cyclization represents a strategy of choice to develop a family of SAPs by reducing the entropy enhancing conformation stabilization. 19 With all these considerations in mind, the aim of the present study is to investigate antibody recognition properties in MS and RTT of a new series of designed short linear and cyclic Antibody Recognition in Multiple Sclerosis and Rett Syndrome 561 synthetic analogs of the N-glucosylated CSF114(Glc). 15,16 In this context, we recently applied the "click chemistry" strategy and performed SAR studies comparing triazolyl-containing cyclopeptides with lactam-and disulfide-bridge analogs, and confirming the biological impact of such cyclizations in different biological contexts.…”

Section: Introductionmentioning

confidence: 99%

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Antibody Recognition in multiple sclerosis and rett syndrome using a collection of linear and cyclic N‐glucosylated antigenic probes

et al. 2015

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Antibody detection in autoimmune disorders, such as multiple sclerosis (MS) and Rett syndrome (RTT) can be achieved more efficiently using synthetic peptides. The previously developed synthetic antigenic probe CSF114(Glc), a type I' β-turn N-glucosylated peptide structure, is able to recognize antibodies in MS and RTT patients' sera as a sign of immune system derangement. We report herein the design, synthesis, conformational analysis, and immunological evaluation of a collection of glycopeptide analogs of CSF114(Glc) to characterize the specific role of secondary structures in MS and RTT antibody recognition. Therefore, we synthesized a series of linear and cyclic short glucosylated sequences, mimicking different β-turn conformations, which were evaluated in inhibition enzyme-linked immunosorbent assays (ELISA). Calculated IC50 ranking analysis allowed the selection of the candidate octapeptide containing two (S)-2-amino-4-pentynoic acid (L-Pra) residues Ac-Pra-RRN(Glc)GHT-Pra-NH2 , with an IC50 in the nanomolar range. This peptide was adequately modified for solid-phase ELISA (SP-ELISA) and surface plasmon resonance (SPR) experiments. Pra-RRN(Glc)GHT-Pra-NH2 peptide was modified with an alkyl chain linked to the N-terminus, favoring immobilization on solid phase in SP-ELISA and differentiating IgG antibody recognition between patients and healthy blood donors with a high specificity. However, this peptide displayed a loss in IgM specificity and sensitivity. Moreover, an analog was obtained after modification of the octapeptide candidate Ac-Pra-RRN(Glc)GHT-Pra-NH2 to favor immobilization on SPR sensor chips. SPR technology allowed us to determine its affinity (KD = 16.4 nM), 2.3 times lower than the affinity of the original glucopeptide CSF114(Glc) (KD = 7.1 nM).

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Section: Peptide Design and Synthesesmentioning

confidence: 99%

Section: Nmr Conformational Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Antibody Recognition in multiple sclerosis and rett syndrome using a collection of linear and cyclic N‐glucosylated antigenic probes

et al. 2015

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“…After optimizations, the intramolecular Suzuki-Miyaura coupling afforded the desired macrocycle 225 in 50% yield. Mallet and co-workers [87] have recently reported the supported synthesis of 1,3-butadiyne constraint cyclopeptides, which could be obtained through an intramolecular Glaser-Eglinton oxidative coupling managed under MW-irradiation. The Glaser coupling occurs between two terminal alkynes, is catalyzed by a Cu(I) salt (usually Cu(OAc)2), and proceeds under mild conditions in presence of a source of nitrogen (such as acetonitrile) and of oxygen (Scheme 47).…”

Section: Scheme 44mentioning

confidence: 99%

Microwave-Assisted Syntheses of Bioactive Seven-Membered, Macro-Sized Heterocycles and Their Fused Derivatives

et al. 2016

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This review describes the recent advances in the microwave-assisted synthesis of 7-membered and larger heterocyclic compounds. Several types of reaction for the cyclization step are discussed: Ring Closing Metathesis (RCM), Heck and Sonogashira reactions, Suzuki-Miyaura cross-coupling, dipolar cycloadditions, multi-component reactions (Ugi, Passerini), etc. Green syntheses and solvent-free procedures have been introduced whenever possible. The syntheses discussed herein have been selected to illustrate the huge potential of microwave in the synthesis of highly functionalized molecules with potential therapeutic applications, in high yields, enhanced reaction rates and increased chemoselectivity, compared to conventional methods. More than 100 references from the recent literature are listed in this review.

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“…7 Moreover, cyclisation strategies that introduce additional conformational rigidity and allow gaining some conformational homogeneity can help in (i) fixing the peptide pharmacophore in a way that maximizes the peptide's interaction with its biological target, and (ii) lowering the intrinsic flexibility of the cyclic peptide. 14 In their study, propargylglycine (Pra) and N-propargylated amino acids were used to achieve cyclisation. In addition, this method would introduce a 1,3-diyne unit as a reactive site for post-cyclisation modification of the peptidomimetic macrocycles.…”

Section: Introductionmentioning

confidence: 99%

Oxidative α,ω-diyne coupling as an approach towards novel peptidic macrocycles

et al. 2015

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The Glaser-Hay diyne coupling proved to be an efficient cyclisation approach towards diyne containing peptidic macrocycles. A variety of tetrapeptide-based macrocyclic 1,3-diynes were obtained from O-propargylated serine or tyrosine residues using Cu(OAc)2·H2O and NiCl2 under an O2-atmosphere. The effect of the linear 1,3-diyne on peptide conformations was studied by NMR and compared with a macrocycle bearing a saturated linker.

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Glaser oxidative coupling on peptides: Stabilization of β-turn structure via a 1,3-butadiyne constraint

Cited by 12 publications

References 37 publications

Antibody Recognition in multiple sclerosis and rett syndrome using a collection of linear and cyclic N‐glucosylated antigenic probes

Antibody Recognition in multiple sclerosis and rett syndrome using a collection of linear and cyclic N‐glucosylated antigenic probes

Microwave-Assisted Syntheses of Bioactive Seven-Membered, Macro-Sized Heterocycles and Their Fused Derivatives

Oxidative α,ω-diyne coupling as an approach towards novel peptidic macrocycles

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