The Bip Method, Based on the Induced Circular Dichroism of a Flexible Biphenyl Probe in Terminally Protected -Bip-Xaa*- Dipeptides, for Assignment of the Absolute Configuration of β-Amino Acids

Dutot, Laurence; Wright, Karen; Gaucher, Anne; Wakselman, Michel; Mazaleyrat, Jean‐Paul; Zotti, Marta De; Peggion, Cristina; Formaggio, Fernando; Toniolo, Claudio

doi:10.1021/ja800059d

Cited by 59 publications

(39 citation statements)

References 35 publications

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“…In an attempt to overcome the low nucleophilicity of TOAC’s amino group towards the acylation reaction during peptide chain elongation, Tominaga et al (2001) described the higher efficiency of incorporation of the β-amino acid POAC (Rassat and Rey 1967) into angiotensin II. Studies of POAC, as well as of β-TOAC, have addressed synthesis, separation, identification, spectroscopic characterization, and absolute configuration assignment of pure enantiomers (Wright et al 2003a, b, 2005, 2008; Péter et al 2003; Dutot et al 2008). The synthesis and conformational characterization of hexapeptides double-labeled with β-TOAC and POAC have also been reported (Wright et al 2007, 2010).…”

Section: Toac and Toac-containing Peptides: Synthesis And Structuralmentioning

confidence: 99%

The spin label amino acid TOAC and its uses in studies of peptides: chemical, physicochemical, spectroscopic, and conformational aspects

et al. 2012

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We review work on the paramagnetic amino acid 2,2,6,6-tetramethyl-N-oxyl-4-amino-4-carboxylic acid, TOAC, and its applications in studies of peptides and peptide synthesis. TOAC was the first spin label probe incorporated in peptides by means of a peptide bond. In view of the rigid character of this cyclic molecule and its attachment to the peptide backbone via a peptide bond, TOAC incorporation has been very useful to analyze backbone dynamics and peptide secondary structure. Many of these studies were performed making use of EPR spectroscopy, but other physical techniques, such as X-ray crystallography, CD, fluorescence, NMR, and FT-IR, have been employed. The use of double-labeled synthetic peptides has allowed the investigation of their secondary structure. A large number of studies have focused on the interaction of peptides, both synthetic and biologically active, with membranes. In the latter case, work has been reported on ligands and fragments of GPCR, host defense peptides, phospholamban, and β-amyloid. EPR studies of macroscopically aligned samples have provided information on the orientation of peptides in membranes. More recent studies have focused on peptide–protein and peptide–nucleic acid interactions. Moreover, TOAC has been shown to be a valuable probe for paramagnetic relaxation enhancement NMR studies of the interaction of labeled peptides with proteins. The growth of the number of TOAC-related publications suggests that this unnatural amino acid will find increasing applications in the future.

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Section: Toac and Toac-containing Peptides: Synthesis And Structuralmentioning

confidence: 99%

The spin label amino acid TOAC and its uses in studies of peptides: chemical, physicochemical, spectroscopic, and conformational aspects

et al. 2012

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“…bond formation with a chiral analyte to generate a CD signal that can be used for absolute configuration and ee determination have been developed by several groups. [44][45][46][47][48][49][50][51][52] Nevertheless, reversible Schiff base formation with chiral amines has become a very popular and highly successful CD sensing strategy. 27,28,30,39,41,53,54 We now wish to report a highly practical method that allows chiroptical ee analysis of a wide range of amines and amino alcohols using an inexpensive commercially available benzaldehyde derivative as probe.…”

Section: Introductionmentioning

confidence: 99%

Stereochemical analysis of chiral amines, diamines, and amino alcohols: Practical chiroptical sensing based on dynamic covalent chemistry

2020

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Practical chiroptical sensing with a small group of commercially available aromatic aldehydes is demonstrated. Schiff base formation between the electron‐deficient 2,4‐dinitrobenzaldehyde probe and either primary amines, diamines, or amino alcohols proceeds smoothly in chloroform at room temperature and is completed in the presence of molecular sieves within 2.5 hours. The substrate binding coincides with a distinct circular dichroism signal induction at approximately 330 nm, which can be correlated to the absolute configuration and enantiomeric composition of the analyte. The usefulness of this sensing method is highlighted with the successful sensing of 18 aliphatic and aromatic amines and amino alcohols and five examples showing quantitative %ee determination with good accuracy.

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“…This chiral induction process yields a Cotton effect that can be correlated to the absolute configuration of the covalently bound substrate. [6][7][8][9][10] Gawronski and colleagues 11,12 and others exploited essentially the same concept for chirality chemosensing by using molecular bevel gears, propellers, 13 or other probes that can afford a CD-active helical arrangement. 14,15 Similarly, Berova and Nakanishi, [16][17][18][19] Anslyn, [20][21][22][23] Canary, 24,25 Borhan, 26,27 and many others have developed a variety of intriguing stereodynamic chemosensors that generate strong CD signals in the presence of a chiral bias.…”

Section: Introductionmentioning

confidence: 99%

Circular Dichroism Sensing of Chiral Compounds Using an Achiral Metal Complex as Probe

Irfanoglu

Wolf

2014

Chirality

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Coordination of a chiral substrate to (meso-salen)cobalt(II) nitrate and subsequent oxidation generates a Co(III) complex exhibiting a strong chiroptical readout that is attributed to spontaneous substrate-to-ligand chirality imprinting. The characteristic circular dichroism (CD) response of the (salen)cobalt complex can be used for enantiomeric analysis of a variety of chiral substrates based on a simple CD measurement at low concentration and without additional purification steps. This chirality sensing approach has potential for high-throughput enantiomeric excess (ee) screening applications and minimizes solvent waste production.

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The Bip Method, Based on the Induced Circular Dichroism of a Flexible Biphenyl Probe in Terminally Protected -Bip-Xaa*- Dipeptides, for Assignment of the Absolute Configuration of β-Amino Acids

Cited by 59 publications

References 35 publications

The spin label amino acid TOAC and its uses in studies of peptides: chemical, physicochemical, spectroscopic, and conformational aspects

The spin label amino acid TOAC and its uses in studies of peptides: chemical, physicochemical, spectroscopic, and conformational aspects

Stereochemical analysis of chiral amines, diamines, and amino alcohols: Practical chiroptical sensing based on dynamic covalent chemistry

Circular Dichroism Sensing of Chiral Compounds Using an Achiral Metal Complex as Probe

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