Synthesis and applications of exo N-((1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl)benzamides as NMR solvating agents for the chiral discrimination of 1,1′-binaphthyl-2,2′-diyl hydrogenphosphates and α-substituted acids

Kannappan, Jayaraman; Jain, Nayan; Bedekar, Ashutosh V.

doi:10.1016/j.tetasy.2015.08.008

Cited by 12 publications

(7 citation statements)

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“…Bedekar et al synthesized modified amides as NMR solvating agents for the chiral discrimination of 1,1′-binaphthyl and alpha -substituted acid enantiomers [ 58 ]. In this procedure, the chiral isobornyl amine 19 was employed, which is readily available and can be used as a starting material to prepare steric bulk amide 20 with three-stereogenic centers for chiral molecular recognition by 31 P-NMR analysis ( Scheme 16 ).…”

Section: 31 P-nmr Chiral Recognitionmentioning

confidence: 99%

Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

Silva

2017

Molecules

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Nuclear magnetic resonance (NMR) is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to 1H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear (19F, 31P, 13C, and 77Se) NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds.

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Section: 31 P-nmr Chiral Recognitionmentioning

confidence: 99%

Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

Silva

2017

Molecules

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“…6 In reported papers, NMR spectroscopy was mainly focused on enantiodifferentiation of chiral analytes with only one chiral center by chiral auxiliaries. 7 However, studies on enantiomeric discrimination of chiral compounds with two or more chiral centers were rarely reported in the past. 8 Nevertheless, these chiral compounds often exist in natural products, chiral drugs, products of asymmetric synthesis and biological systems.…”

Section: Introductionmentioning

confidence: 99%

Discrimination of enantiomers of dipeptide derivatives with two chiral centers by tetraaza macrocyclic chiral solvating agents using¹H NMR spectroscopy

Fang

Guo

et al. 2016

Org. Chem. Front.

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1H NMR spectroscopy is often used to discriminate enantiomers of chiral analytes and determine their enantiomeric excess (ee) by various chiral auxiliaries. In reported research, these studies were mainly focused on chiral discriminantion of chiral analytes with only one chiral center. However, many chiral compounds possessing two or more chiral centers are often found in natural products, chiral drugs, products of asymmetric synthesis and biological systems. Therefore, it is necessary to investigate their chiral discrimination by effective chiral auxiliaries using 1H NMR spectroscopy. In this paper, a new class of tetraaza macrocyclic chiral solvating agents (TAMCSAs) with two amide (CONH), two amino (NH) and two phenolic hydroxyl (PhOH) groups has been designed and synthsized for chiral discrimination towards dipeptide derivatives with two chiral centers. These dipeptide derivatives are important chiral species because some of them are used as clinical drugs and special dietary supplements for treatment of human diseases, such as L-alanyl-L-glutamine and aspartame. The results show that these TAMCSAs have excellent chiral discriminating properties and offer multiple detection possibilities pertaining to 1H NMR signals of diagnostic split protons. The nonequivalent chemical shifts (up to 0.486 ppm) of various types of protons of these dipeptide derivatives were evaluated with the assistance of well-resolved 1H NMR signals in most cases. In addition, enantiomeric excesses (ee) of the dipeptide derivatives with different optical compositions have been calculated based on integration of well-separeted proton signals. At the same time, the possible chiral discriminating behaviors have been discussed by means of Job plots, ESI mass spectra and a proposed theoretical model of (±)-G1 with TAMCSA 1c. Additionally, the association constants of enantiomers of (±)-G5 with TAMCSA 1a were calculated by employing the nonlinear curve-fitting method.

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“…The principle of the separation of signals for the enantiomers of the analyte is based on supramolecular interactions with the chiral additive such as hydrogen bonding, C-HÁ Á Á,interactions, etc. We have recently reported a chiral camphor-based Kagan's amide and explored its activity for estimation of enantiomer ratios of a wide variety of functionalized molecules (Kannappan et al, 2015(Kannappan et al, , 2017. As part of our ongoing studies in this area, we now report the synthesis and structure of the title compound (Fig.…”

Section: Structure Descriptionmentioning

confidence: 99%

5-Nitro-N ²,N ³-bis[(1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl]isophthalamide dichloromethane hemisolvate

et al. 2018

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Synthesis and applications of exo N-((1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl)benzamides as NMR solvating agents for the chiral discrimination of 1,1′-binaphthyl-2,2′-diyl hydrogenphosphates and α-substituted acids

Cited by 12 publications

References 82 publications

Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

Discrimination of enantiomers of dipeptide derivatives with two chiral centers by tetraaza macrocyclic chiral solvating agents using¹H NMR spectroscopy

5-Nitro-N ²,N ³-bis[(1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl]isophthalamide dichloromethane hemisolvate

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Synthesis and applications of exo N-((1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl)benzamides as NMR solvating agents for the chiral discrimination of 1,1′-binaphthyl-2,2′-diyl hydrogenphosphates and α-substituted acids

Cited by 12 publications

References 82 publications

Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

Discrimination of enantiomers of dipeptide derivatives with two chiral centers by tetraaza macrocyclic chiral solvating agents using1H NMR spectroscopy

5-Nitro-N 2,N 3-bis[(1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl]isophthalamide dichloromethane hemisolvate

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Discrimination of enantiomers of dipeptide derivatives with two chiral centers by tetraaza macrocyclic chiral solvating agents using¹H NMR spectroscopy

5-Nitro-N ²,N ³-bis[(1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl]isophthalamide dichloromethane hemisolvate