Group IVA organometallic reagents.  2.  Enantiomeric purity determination of 1,2-diols through NMR spectroscopy without chiral auxiliaries

Luchinat, Claudio; Roelens, Stefano

doi:10.1021/ja00276a027

Cited by 44 publications

(18 citation statements)

References 2 publications

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“…3b; equation A) obtained by a modification of the reported equation (Fig. 3b)5556 (for details, see Supplementary Methods), suggesting no preference in the diastereomeric duplex formation, thus forming the homochiral and heterochiral 1a 2 duplexes in a 2:1 molar ratio in CDCl 3 at 25 °C. As anticipated, however, the diastereomeric duplex formation is sensitive to temperature and its molar ratio changed on heating or cooling (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 95%

Chirality- and sequence-selective successive self-sorting via specific homo- and complementary-duplex formations

et al. 2015

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Self-recognition and self-discrimination within complex mixtures are of fundamental importance in biological systems, which entirely rely on the preprogrammed monomer sequences and homochirality of biological macromolecules. Here we report artificial chirality- and sequence-selective successive self-sorting of chiral dimeric strands bearing carboxylic acid or amidine groups joined by chiral amide linkers with different sequences through homo- and complementary-duplex formations. A mixture of carboxylic acid dimers linked by racemic-1,2-cyclohexane bis-amides with different amide sequences (NHCO or CONH) self-associate to form homoduplexes in a completely sequence-selective way, the structures of which are different from each other depending on the linker amide sequences. The further addition of an enantiopure amide-linked amidine dimer to a mixture of the racemic carboxylic acid dimers resulted in the formation of a single optically pure complementary duplex with a 100% diastereoselectivity and complete sequence specificity stabilized by the amidinium–carboxylate salt bridges, leading to the perfect chirality- and sequence-selective duplex formation.

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Section: Resultsmentioning

confidence: 95%

Chirality- and sequence-selective successive self-sorting via specific homo- and complementary-duplex formations

et al. 2015

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“…A few other examples of SIDA active compounds have been reported: alkylphenylphosphinic amides, phosphinic acids, phosphinothioic acids, 2‐anilino‐2‐oxo‐1,3,2‐oxazaphosphorinanes, dioxastannolanes, 1,5‐benzothiazepines, methanephosphonic acid diamides, carboxylic acids, carboxamides, perylene bisimides and chiral ruthenium bipyridine complexes . Interestingly, the phenomenon was reported for several natural products …”

Section: Figurementioning

confidence: 89%

Attracting Enantiomers: Chiral Analytes That Are Simultaneously Shift Reagents Allow Rapid Screening of Enantiomeric Ratios by NMR Spectroscopy

Storch

Haas

Trapp

2017

Chemistry A European J

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The rapid and direct determination of enantiomeric ratios is of increasing interest due to the significantly reduced effort compared to chromatographic methods and the large number of analytes, for instance in enantioselective catalysis. Current strategies include colorimetric assays, (a)chiral solvating reagents for NMR spectroscopy and metal complexes for CD sensing. We report the determination of enantiomeric ratios based on the self-induced diastereomeric anisochronism (SIDA) effect. Alanine derivatives that represent chiral products of enantioselective catalysis, such as the well-established hydrogenation of dehydroamino acids, were investigated. The SIDA effect was significantly enhanced by attachment of 3,5-dinitrobenzoyl π-π interactions sites. This simple modification enabled simultaneous determination of enantiomeric ratios and conversions by NMR spectroscopy.

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“…[6,7] The chiral self-discrimination phenomenon was first observed by Uskokovic and coworkers in dihydroquinine in 1969. [8] Since then, self-discrimination has been found in a variety of chiral compounds, such as phosphorus acid derivatives, [9 -12] 2-substituted-1,2-glycols, [13] phosphonate of alcohols, [14] amino acid derivatives, [15] diols, [16] carboxamides, [17] 2-anilino-2-oxo-1,3,2-oxazaphosphorinanes, [18] 3-mercaptoderivatives of 2-bromopropanoic acid, [19] and so on. It is generally recognized that inter-molecular hydrogen-bonding (HB) interaction plays an important role in self-recognition.…”

Section: Introductionmentioning

confidence: 99%

Chiral self‐discrimination of the enantiomers of α‐phenylethylamine derivatives in proton NMR

Huang

Bai

Feng

2009

Magnetic Reson in Chemistry

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Two types of chiral analytes, the urea and amide derivatives of alpha-phenylethylamine, were prepared. The effect of inter-molecular hydrogen-bonding interaction on self-discrimination of the enantiomers of analytes has been investigated using high-resolution (1)H NMR. It was found that the urea derivatives with double-hydrogen-bonding interaction exhibit not only the stronger hydrogen-bonding interaction but also better self-recognition abilities than the amide derivatives (except for one bearing two NO(2) groups). The present results suggest that double-hydrogen-bonding interaction promotes the self-discrimination ability of the chiral compounds.

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Group IVA organometallic reagents. 2. Enantiomeric purity determination of 1,2-diols through NMR spectroscopy without chiral auxiliaries

Cited by 44 publications

References 2 publications

Chirality- and sequence-selective successive self-sorting via specific homo- and complementary-duplex formations

Chirality- and sequence-selective successive self-sorting via specific homo- and complementary-duplex formations

Attracting Enantiomers: Chiral Analytes That Are Simultaneously Shift Reagents Allow Rapid Screening of Enantiomeric Ratios by NMR Spectroscopy

Chiral self‐discrimination of the enantiomers of α‐phenylethylamine derivatives in proton NMR

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