Abstract
This chapter will describe the general features and main categories of chiral solvating agents (CSAs) for NMR spectroscopy, spanning from low-medium sized CSAs to macrocyclic ones. CSAs based on chiral ionic liquids (CILs) will be introduced in view of their increasing popularity, and, finally, a short paragraph will be dedicated to special applications of CSAs in particular experimental conditions. Several valuable works, which are mainly devoted to investigate enantiodifferentiation mechanisms by NMR, will not be discussed. The main objective is to identify the current trend in the research areas dedicated to the development of new CSAs for NMR spectroscopy.
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References
Raban M, Mislow K (1965) Determination of optical purity by nuclear magnetic resonance spectroscopy. Tetrahedron Lett 6:4249–4253
Pirkle WH (1966) The nonequivalence of physical properties of enantiomers in optically active solvents. Differences in nuclear magnetic resonance spectra. I. J Am Chem Soc 88:1837
Raban M, Mislow K (1967) Modern methods for the determination of optical purity. Top Stereochem 2:199–230
Dale JA, Mosher HS (1968) Nuclear magnetic resonance nonequivalence of diastereoisomeric esters of α-substituted phenylacetic acids for the determination of stereochemical purity. J Am Chem Soc 90:3732–3738
Campbell J (1972) Determination of optical and enantiomeric purity by nuclear magnetic resonance spectroscopy (NMR). Aldrichimica Acta 5:29–32
Sullivan GR (1978) Chiral lanthanide shift reagents. Top Stereochem 10:287–329
Pirkle WH, Hoover DJ (1982) NMR chiral solvating agents. Top Stereochem 13:263–331
Yamaguchi S (1983) Nuclear magnetic resonance analysis using chiral derivatives. In: Morrison JD (ed) Asymmetric synthesis, vol 1. Academic, New York, pp 125–152
Fraser RR (1983) Nuclear magnetic resonance analysis using chiral shift reagents. In: Morrison JD (ed) Asymmetric synthesis, vol 1. Academic, New York, pp 173–196
Weisman GR (1983) Nuclear magnetic resonance analysis using chiral solvating agents. In: Morrison JD (ed) Asymmetric synthesis, vol 1. Academic, New York, pp 153–171
Schurig V (1985) Current methods for determination of enantiomeric compositions. Part 2. NMR spectroscopy with chiral lanthanide shift reagents. Kontakte (Darmstadt) 22–36
Aboul-Enein HY (1988) NMR methods for optical purity determination of pharmaceuticals. Anal Lett 21:2155–2163
Parker D (1991) NMR determination of enantiomeric purity. Chem Rev 91:1441–1457
Casy AF (1983) Chiral discrimination by NMR spectroscopy. Trends Anal Chem 12:185–189
Hulst R, Kellogg RM, Feringa BL (1995) New methodologies for enantiomeric excess (ee) determination based on phosphorus NMR. Rec Trav Chim Pays Bas 114:115–138
Rothchild R (2000) NMR methods for determination of enantiomeric excess. Enantiomer 5:457–471
Wenzel TJ (2007) Discrimination of chiral compounds using NMR spectroscopy. Wiley, New York
Wenzel TJ, Wilcox JD (2003) Chiral reagents for the determination of enantiomeric excess and absolute configuration using NMR spectroscopy. Chirality 15:256–270
Uccello-Barretta G, Balzano F, Salvadori P (2006) Enantiodiscrimination by NMR spectroscopy. Curr Pharm Des 12:4023–4045
Kumar AP, Jin D, Lee Y-I (2009) Recent development on spectroscopic methods for chiral analysis of enantiomeric compounds. Appl Spectrosc Rev 44:267–316
Yip Y, Wong S, Choi S (2011) Assessment of the chemical and enantiomeric purity of organic reference materials. Trends Anal Chem 30:628–640
Wenzel TJ, Chisholm CD (2011) Using NMR spectroscopic methods to determine enantiomeric purity and assign absolute stereochemistry. Prog Nucl Magn Reson Spectrosc 59:1–63
Brevard C (1983) The multinuclear approach to NMR spectroscopy. Reidel Publishing Company, Boston, pp 1–27
Klika KD (2009) Use of sub-stoichiometric amounts of chiral auxiliaries for enantiodifferentiation by NMR; caveats and potential utility. Tetrahedron Asymmetry 20:1099–1102
Pirkle WH, Sikkenga DL (1977) The use of chiral solvating agent for nuclear magnetic resonance determination of enantiomeric purity and absolute configuration of lactones. Consequences of three-point interactions. J Org Chem 42:1370–1374
Pirkle WH, Rinaldi PL (1977) Nuclear magnetic resonance determination of enantiomeric compositions of oxaziridines using chiral solvating agents. J Org Chem 42:3217–3219
Isiklan M, Asmafiliz N, Ozalp EE, Ilter EE, Kilic Z, Cosut B, Yesilot S, Kilic A, Ozturk A, Hokelek T, Koc Bilir LY, Acik L, Akyuz E (2010) Phosphorus–nitrogen compounds. 21. Syntheses, structural investigations, biological activities, and DNA interactions of new N/O spirocyclic phosphazene derivatives. The NMR behaviors of chiral phosphazenes with stereogenic centers upon the addition of chiral solvating agents. Inorg Chem 49:7057–7071
Cosut B, Ibisoglu H, Kilic A, Yesilot S (2009) Synthesis and enantiomeric analysis of cyclotriphosphazene derivatives with one center of chirality. Inorg Chim Acta 362:4931–4936
Coles SJ, Davies DB, Eaton RJ, Hursthouse MB, Kilic A, Shaw RA, Uslu A (2006) The structural and stereogenic properties of pentaerythritoxy-bridged cyclotriphosphazene derivatives: spiro–spiro, spiro–ansa and ansa–ansa isomers. Dalton Trans 1302–1312
Lao KYY, Hodgson DJ, Dawson B, Buist PH (2005) A micromethod for the stereochemical analysis of fatty acid desaturase-mediated sulfoxidation reactions. Bioorg Med Chem Lett 15:2799–2802
Tremblay AE, Tan N, Whittle E, Hodgson DJ, Dawson B, Buist PH, Shanklin J (2010) Stereochemistry of 10-sulfoxidation catalyzed by a soluble Δ9 desaturase. Org Biomol Chem 8:1322–1328
Tremblay AE, Lao KYY, Hodgson DJ, Dawson B, Buist PH (2009) Synthesis of chiral fluorine-tagged reference standards for the 19F NMR-based stereochemical analysis of sulfoxides at trace analytical levels. Bioorg Med Chem Lett 19:5146–5150
De Moragas M, Cervello E, Port A, Jaime C, Virgili A, Ancian B (1998) Behavior of the 9-anthryl-tert-butylcarbinol as a chiral solvating agent. Study of diastereochemical association by intermolecular NOE and molecular dynamics calculations. J Org Chem 63:8689–8695
Gil J, Virgili A (1999) The first chiral solvating agent (CSA) without 1H NMR signals: the perdeuterio-2,2,2-trifluoro-1-(9-anthryl)ethanol. Preparation and chiral induction on protonated Pirkle alcohol. J Org Chem 64:7274–7276
Perez-Trujillo M, Virgili A, Molins E (2004) Preparation, conformational analysis and behavior as chiral solvating agents of 9-anthrylpentafluorophenylmethanol enantiomers: study of the diastereomeric association. Tetrahedron Asymmetry 15:1615–1621
Sanchez-Aris M, Estivill C, Virgili A (2003) Synthesis and structural study of the enantiomers of α, α′-bis(trifluoromethyl)-10,10′-(9,9′-bianthryl)dimethanol as a chiral solvating agent. Tetrahedron Asymmetry 14:3129–3135
Munoz A, Virgili A (2002) Preparation and behavior of (R)- and (S)-2,2,2-trifluoro-1-(1-pyrenyl)ethanol as chiral solvating agents: study of the diastereomeric association by Job’s plots, intermolecular NOE and binding constants. Tetrahedron Asymmetry 13:1529–1534
Benson SC, Cai P, Colon M, Haiza MA, Tokles M, Snyder JK (1988) Use of carboxylic acids as chiral solvating agents for the determination of optical purity of chiral amines by NMR spectroscopy. J Org Chem 53:5335–5341
Buist PH, Marecak D (1995) (S)-α-Methoxyphenyl acetic acid: a new NMR chiral shift reagent for the stereochemical analysis of sulfoxides. Tetrahedron Asymmetry 6:7–10
Haiza MA, Sanyal A, Snyder JK (1997) O-Nitromandelic acid: a chiral solvating agent for the NMR determination of chiral diamine enantiomeric purity. Chirality 9:556–562
Cavalluzzi MM, Bruno C, Lentini G, Lovece A, Catalano A, Carocci A, Franchini C (2009) One-step synthesis of homochiral O-aryl and O-heteroaryl mandelic acids and their use as efficient 1H NMR chiral solvating agents. Tetrahedron Asymmetry 20:1984–1991
Fauconnot L, Nugier-Chauvin C, Noiret N, Patin H (1997) Enantiomeric excess determination of some chiral sulfoxides by NMR: use of (S)-ibuprofen and (S)-naproxen as shift reagents. Tetrahedron Lett 38:7875–7878
Demchuk OM, Swierczynska W, Michal Pietrusiewicz K, Woznica M, Wojcik D, Frelek J (2008) A convenient application of the NMR and CD methodologies for the determination of enantiomeric ratio and absolute configuration of chiral atropoisomeric phosphine oxides. Tetrahedron Asymmetry 19:2339–2345
Chinchilla R, Foubelo F, Najera C, Yus M (1995) (R)-O-Aryllactic acids: convenient chiral solvating agents for direct 1H NMR determination of the enantiomeric composition of amines and aminoalcohols. Tetrahedron Asymmetry 6:1877–1880
Faigl F, Thurner A, Tarkanyi G, Kovari J, Mordini A (2002) Resolution and enantioselective rearrangements of amino group-containing oxiranyl ethers. Tetrahedron Asymmetry 13:59–68
Przybyl AK, Kubicki M (2011) Simple and highly efficient preparation and characterization of (−)-lupanine and (+)-sparteine. Tetrahedron 67:7787–7793
Michalik M, Doebler C (1990) Determination of the chiral purity of amino alcohols by proton NMR spectroscopy. Tetrahedron 46:7739–7744
Iuliano A, Bartalucci D, Uccello-Barretta G, Balzano F, Salvadori P (2001) 3,5-Dinitrobenzoylphenylglycine analogues bearing the 1,1′-binaphthalene moiety – synthesis, conformational study, and application as chiral solvating agents. Eur J Org Chem 2177–2184
Ardej-Jakubisiak M, Kawecki R (2008) NMR method for determination of enantiomeric purity of sulfinimines. Tetrahedron Asymmetry 19:2645–2647
Salsbury JS, Isbester PK (2005) Quantitative 1H NMR method for the routine spectroscopic determination of enantiomeric purity of active pharmaceutical ingredients fenfluramine, sertraline, and paroxetine. Magn Reson Chem 43:910–917
Redondo J, Capdevila A, Latorre I (2010) Use of (S)-BINOL as NMR chiral solvating agent for the enantiodiscrimination of omeprazole and its analogs. Chirality 22:472–478
Klika KD, Budovska M, Kutschy P (2010) Enantiodifferentiation of phytoalexin spirobrassinin derivatives using the chiral solvating agent (R)-(+)-1,1′-bi-2-naphthol in conjunction with molecular modeling. Tetrahedron Asymmetry 21:647–658
Toda F, Mori K, Okada J, Node M, Itoh A, Oomine K, Fuji K (1988) New chiral shift reagents, optically active 2,2′-dihydroxy-1,1′-binaphthyl and 1,6-bis(o-chlorophenyl)-1,6-diphenyl-2,4-hexadiyne-1,6-diol. Chem Lett 131–134
Drabowicz J, Duddeck H (1989) Proton NMR spectral nonequivalence of sulfoxide enantiomers in the presence of 2,2′-dihydroxy-1,1′-binaphthyl. Sulfur Lett 10:37–40
Ma Q, Ma M, Tian H, Ye X, Xiao H, Chen L, Lei X (2012) A novel amine receptor based on the binol scaffold functions as a highly effective chiral shift reagent for carboxylic acids. Org Lett 14:5813–5815
Omelanczuk J, Mikolajczyk M (1996) Chiral t-butylphenylphosphinothioic acid: a useful chiral solvating agent for direct determination of enantiomeric purity of alcohols, thiols, amines, diols, amino alcohols, and related compounds. Tetrahedron Asymmetry 7:2687–2694
Drabowicz J, Budzinski B, Mikolajczyk M (1992) Chiral tert-butylphenylphosphinothioic acid: a new NMR solvating agent for determination of enantiomeric excesses of sulfoxides. Tetrahedron Asymmetry 3:1231–1234
Gulea M, Kwiatkowska M, Lyzwa P, Legay R, Gaumont A-C, Kielbasinski P (2009) Michael addition to a chiral non-racemic 2-phosphono-2,3-didehydrothiolane S-oxide. Tetrahedron Asymmetry 20:293–297
Mucha P, Mloston G, Jasinski M, Linden A, Heimgartner H (2008) A new approach to enantiomerically pure bis-imidazoles derived from trans-1,2-diaminocyclohexane. Tetrahedron Asymmetry 19:1600–1607
Szawkalo J, Zawadzka A, Wojtasiewicz K, Leniewski A, Drabowicz J, Czarnocki Z (2005) First enantioselective synthesis of the antitumour alkaloid (+)-crispine A and determination of its enantiomeric purity by 1H NMR. Tetrahedron Asymmetry 16:3619–3621
Louafi F, Moreau J, Shahane S, Golhen S, Roisnel T, Sinbandhit S, Hurvois J-P (2011) Electrochemical synthesis and chemistry of chiral 1-cyanotetrahydroisoquinolines. An approach to the asymmetric syntheses of the alkaloid (−)-crispine A and its natural (+)-antipode. J Org Chem 76:9720–9732
Czarnocki SJ, Wojtasiewicz K, Jozwiak AP, Maurin JK, Czarnocki Z, Drabowicz J (2008) Enantioselective synthesis of (+)-trypargine and (+)-crispine E. Tetrahedron 64:3176–3182
Maier NM, Zoltewicz JA (1997) Dynamic equilibration of diastereomeric salts of atropisomers. Proton NMR spectra of 1,8-di(3′-pyridyl)naphthalene in the presence of R-camphorsulfonic acid. Tetrahedron 53:465–468
Satishkumar S, Periasamy M (2009) Chiral recognition of carboxylic acids by Troeger’s base derivatives. Tetrahedron Asymmetry 20:2257–2262
Deshmukh M, Dunach E, Juge S, Kagan HB (1984) A convenient family of chiral shift reagents for measurement of enantiomeric excesses of sulfoxides. Tetrahedron Lett 25:3467–3470
Pakulski Z, Demchuk OM, Kwiatosz R, Osinski PW, Swierczynska W, Pietrusiewicz KM (2003) The classical Kagan’s amides are still practical NMR chiral shift reagents: determination of enantiomeric purity of P-chirogenic phospholene oxides. Tetrahedron Asymmetry 14:1459–1462
Hirose T, Naito K, Shitara H, Nohira H, Baldwin BW (2001) 1H NMR study of chiral recognition of amines by chiral Kemp’s acid diamide. Tetrahedron Asymmetry 12:375–380
Hirose T, Naito K, Nakahara M, Shitara H, Aoki Y, Nohira H, Baldwin BW (2002) New chiral Kemp’s acid diamides for chiral amine recognition by 1H NMR. J Incl Phenom Macrocycl Chem 43:87–93
Bergmann H, Grosch B, Sitterberg S, Bach T (2004) An enantiomerically pure 1,5,7-trimethyl-3-azabicyclo[3.3.1]nonan-2-one as 1H NMR shift reagent for the ee determination of chiral lactams, quinolones, and oxazolidinones. J Org Chem 69:970–973
Yang X, Wang G, Zhong C, Wu X, Fu E (2006) Novel NMR chiral solvating agents derived from (1R,2R)-diaminocyclohexane: synthesis and enantiodiscrimination for chiral carboxylic acids. Tetrahedron Asymmetry 17:916–921
Luo Z, Zhong C, Wu X, Fu E (2008) Amphiphilic chiral receptor as efficient chiral solvating agent for both lipophilic and hydrophilic carboxylic acids. Tetrahedron Lett 49:3385–3390
Luo Z, Li B, Fang X, Hu K, Wu X, Fu E (2007) Novel chiral solvating agents derived from natural amino acid: enantiodiscrimination for chiral α-arylalkylamines. Tetrahedron Lett 48:1753–1756
Naziroglu HN, Durmaz M, Bozkurt S, Sirit A (2011) Application of l-proline derivatives as chiral shift reagents for enantiomeric recognition of carboxylic acids. Chirality 23:463–471
Wagger J, Grdadolnik SG, Groselj U, Meden A, Stanovnik B, Svete J (2007) Chiral solvating properties of (S)-1-benzyl-6-methylpiperazine-2,5-dione. Tetrahedron Asymmetry 18:464–475
Malavasic C, Wagger J, Stanovnik B, Svete J (2008) (S)-N-Benzyl-3(6)-methylpiperazine-2,5-diones as chiral solvating agents for N-acylamino acid esters. Tetrahedron Asymmetry 19:1557–1567
Malavasic C, Stanovnik B, Wagger J, Svete J (2011) The effect of substituents on the chiral solvating properties of (S)-1,6-dialkylpiperazine-2,5-diones. Tetrahedron Asymmetry 22:1364–1371
Kim S, Choi K (2011) A practical solvating agent for the chiral NMR discrimination of carboxylic acids. Eur J Org Chem 4747–4750
Bozkurt S, Durmaz M, Naziroglu HN, Yilmaz M, Sirit A (2011) Amino alcohol based chiral solvating agents: synthesis and applications in the NMR enantiodiscrimination of carboxylic acids. Tetrahedron Asymmetry 22:541–549
Ma F, Ai L, Shen X, Zhang C (2007) New macrocyclic compound as chiral shift reagent for carboxylic acids. Org Lett 9:125–127
Wang W, Ma F, Shen X, Zhang C (2007) New chiral auxiliaries derived from (S)-α-phenylethylamine as chiral solvating agents for carboxylic acids. Tetrahedron Asymmetry 18:832–837
Wang W, Shen X, Ma F, Li Z, Zhang C (2008) Chiral amino alcohols derived from natural amino acids as chiral solvating agents for carboxylic acids. Tetrahedron Asymmetry 19:1193–1199
Li Y, Raushel FM (2007) Differentiation of chiral phosphorus enantiomers by 31P and 1H NMR spectroscopy using amino acid derivatives as chemical solvating agents. Tetrahedron Asymmetry 18:1391–1397
Hernandez-Rodriguez M, Juaristi E (2007) Structurally simple chiral thioureas as chiral solvating agents in the enantiodiscrimination of α-hydroxy and α-amino carboxylic acids. Tetrahedron 63:7673–7678
Lacour J (2010) Chiral hexacoordinated phosphates: from pioneering studies to modern uses in stereochemistry. C R Chim 13:985–997
Bergman SD, Frantz R, Gut D, Kol M, Lacour J (2006) Effective chiral recognition among ions in polar media. Chem Commun 850–852
Michon C, Goncalves-Farbos M-H, Lacour J (2009) NMR enantiodifferentiation of quaternary ammonium salts of Troeger base. Chirality 21:809–817
Lacour J, Goujon-Ginglinger C, Troche-Haldimann S, Jordry JJ (2000) Efficient enantioselective extraction of tris(diimine)ruthenium(II) complexes by chiral, lipophilic TRISPHAT anions. Angew Chem Int Ed 39:3695–3697
Payet E, Dimitrov-Raytchev P, Chatelet B, Guy L, Grass S, Lacour J, Dutasta J-P, Martinez A (2012) Absolute configuration and enantiodifferentiation of a hemicryptophane incorporating an azaphosphatrane moiety. Chirality 24:1077–1081
Barry NPE, Austeri M, Lacour J, Therrien B (2009) Highly efficient NMR enantiodiscrimination of chiral octanuclear metalla-boxes in polar solvent. Organometallics 28:4894–4897
Perollier C, Bernardinelli G, Lacour J (2008) Sugar derived hexacoordinated phosphates: chiral anionic auxiliaries with general asymmetric efficiency. Chirality 20:313–324
Llewellyn DB, Arndtsen BA (2003) The use of a chiral borate counteranion as a 1H NMR shift reagent for cationic copper(I) complexes. Can J Chem 81:1280–1284
Loewer Y, Weiss C, Biju AT, Froehlich R, Glorius F (2011) Synthesis and application of a chiral diborate. J Org Chem 76:2324–2327
Moon LS, Jolly RS, Kasetti Y, Bharatam PV (2009) A new chiral shift reagent for the determination of enantiomeric excess and absolute configuration in cyanohydrins. Chem Commun 1067–1069
Moon LS, Pal M, Kasetti Y, Bharatam PV, Jolly RS (2010) Chiral solvating agents for cyanohydrins and carboxylic acids. J Org Chem 75:5487–5498
Pirkle WH, Pochapsky TC (1987) Chiral molecular recognition in small bimolecular systems: a spectroscopic investigation into the nature of diastereomeric complexes. J Am Chem Soc 109:5975–5982
Salvadori P, Rosini C, Pini D, Bertucci C, Altemura P, Uccello-Barretta G, Raffaelli A (1987) A novel application of Cinchona alkaloids as chiral auxiliaries: preparation and use of a new family of chiral stationary phases for the chromatographic resolution of racemates. Tetrahedron 43:4969–4978
Uccello-Barretta G, Rosini C, Pini D, Salvadori P (1990) A spectroscopic study of the interaction of (d)- and (l)-N-(3,5-dinitrobenzoyl)valine methyl ester with n-butylamide of (S)-2-[(phenylcarbamoyl)oxy]propionic acid: direct evidence for a chromatographic chiral recognition rationale. J Am Chem Soc 112:2707–2710
Pirkle WH, Tsipouras A (1985) 3,5-Dinitrobenzoyl amino acid esters. Broadly applicable chiral solvating agents for NMR determination of enantiomeric purity. Tetrahedron Lett 26:2989–2992
Rosini C, Uccello-Barretta G, Pini D, Abete C, Salvadori P (1988) Quinine: an inexpensive chiral solvating agent for the determination of enantiomeric composition of binaphthyl derivatives and alkylarylcarbinols by NMR spectroscopy. J Org Chem 53:4579–4581
Salvadori P, Pini D, Rosini C, Bertucci C, Uccello-Barretta G (1992) Chiral discriminations with Cinchona alkaloids. Chirality 4:43–49
Uccello-Barretta G, Pini D, Mastantuono A, Salvadori P (1995) Direct NMR assay of enantiomeric purity of chiral β-hydroxy esters by using quinine as chiral solvating agent. Tetrahedron Asymmetry 6:1965–1972
Maly A, Lejczak B, Kafarski P (2003) Quinine as chiral discriminator for determination of enantiomeric excess of diethyl 1,2-dihydroxyalkanephosphonates. Tetrahedron Asymmetry 14:1019–1024
Uccello-Barretta G, Bardoni S, Balzano F, Salvadori P (2001) Versatile chiral auxiliaries for NMR spectroscopy based on carbamoyl derivatives of dihydroquinine. Tetrahedron Asymmetry 12:2019–2023
Uccello-Barretta G, Mirabella F, Balzano F, Salvadori P (2003) C11 versus C9 carbamoylation of quinine: a new class of versatile polyfunctional chiral solvating agents. Tetrahedron Asymmetry 14:1511–1516
Pini D, Uccello-Barretta G, Rosini C, Salvadori P (1991) N-(n-Butylamide) of (S)-2-(phenylcarbamoyloxy)propionic acid: a new chiral solvating agent, derived from l-lactic acid, for the enantiomeric purity determination of derivatized amino acids. Chirality 3:174–176
Heo KS, Hyun MH, Cho YJ, Ryoo JJ (2011) Determination of optical purity of 3,5-dimethoxybenzoyl-leucine diethylamide by chiral chromatography and 1H and 13C NMR spectroscopy. Chirality 23:281–286
Pirkle WH, Welch CJ, Lamm B (1992) Design, synthesis, and evaluation of an improved enantioselective naproxen selector. J Org Chem 57:3854–3860
Pirkle WH, Welch CJ (1992) An improved chiral stationary phase for the chromatographic separation of underivatized naproxen enantiomers. J Liq Chromatogr 15:1947–1955
Iwaniuk DP, Wolf C (2010) A versatile and practical solvating agent for enantioselective recognition and NMR analysis of protected amines. J Org Chem 75:6724–6727
Palomino-Schaetzlein M, Virgili A, Gil S, Jaime C (2006) Di-(R,R)-1-[10-(1-hydroxy-2,2,2-trifluoroethyl)-9-anthryl]-2,2,2-trifluoroethyl muconate: a highly chiral cavity for enantiodiscrimination by NMR. J Org Chem 71:8114–8120
Gil S, Palomino-Schaetzlein M, Burusco KK, Jaime C, Virgili A (2010) Molecular tweezers for enantiodiscrimination in NMR: di-(R,R)-1-[10-(1-hydroxy-2,2,2-trifluoroethyl)-9-anthryl]-2,2,2-trifluoroethyl benzenedicarboxylates. Chirality 22:548–556
Pena C, Gonzalez-Sabin J, Alfonso I, Rebolledo F, Gotor V (2007) New pincer-like receptor derived from trans-cyclopentane-1,2-diamine as a chiral shift reagent for carboxylic acids. Tetrahedron Asymmetry 18:1981–1985
Pena C, Gonzalez-Sabin J, Alfonso I, Rebolledo F, Gotor V (2008) Cycloalkane-1,2-diamine derivatives as chiral solvating agents. Study of the structural variables controlling the NMR enantiodiscrimination of chiral carboxylic acids. Tetrahedron 64:7709–7717
Liu L, Ye M, Hu X, Yu X, Zhang L, Lei X (2011) Chiral solvating agents for carboxylic acids based on the salen moiety. Tetrahedron Asymmetry 22:1667–1671
Altava B, Burguete MI, Carbo N, Escorihuela J, Luis SV (2010) Chiral bis(amino amides) as chiral solvating agents for enantiomeric excess determination of α-hydroxy and arylpropionic acids. Tetrahedron Asymmetry 21:982–989
Legouin B, Gayral M, Uriac P, Tomasi S, van de Weghe P (2010) Recognition of enantiomers with chiral molecular tweezers derived from (+)- or (−)-usnic acid. Tetrahedron Asymmetry 21:1307–1310
Ema T, Ouchi N, Doi T, Korenaga T, Sakai T (2005) Highly sensitive chiral shift reagent bearing two zinc porphyrins. Org Lett 7:3985–3988
Williams T, Pitcher RG, Bommer P, Gutzwiller J, Uskokovic M (1969) Diastereomeric solute–solute interactions of enantiomers in achiral solvents. Nonequivalence of the nuclear magnetic resonance spectra of racemic and optically active dihydroquinine. J Am Chem Soc 91:1871–1872
Uccello-Barretta G, Vanni L, Balzano F (2009) NMR enantiodiscrimination phenomena by quinine C9-carbamates. Eur J Org Chem 860–869
Uccello-Barretta G, Balzano F, Salvadori P (2005) Rationalization of the multireceptorial character of chiral solvating agents based on quinine and its derivatives: overview of selected NMR investigations. Chirality 17:S243–S248
Uccello-Barretta G, Vanni L, Berni MG, Balzano F (2011) NMR enantiodiscrimination by pentafluorophenylcarbamoyl derivatives of quinine: C10 versus C9 derivatization. Chirality 23:417–423
Abid M, Toeroek B (2005) Cinchona alkaloid induced chiral discrimination for the determination of the enantiomeric composition of α-trifluoromethylated-hydroxyl compounds by 19F NMR spectroscopy. Tetrahedron Asymmetry 16:1547–1555
Zymanczyk-Duda E, Skwarczynski M, Lejczak B, Kafarski P (1996) Accurate assay of enantiopurity of 1-hydroxy- and 2-hydroxyalkylphosphonate esters. Tetrahedron Asymmetry 7:1277–1280
Rudzinska E, Berlicki L, Kafarski P, Lammerhofer M, Mucha A (2009) Cinchona alkaloids as privileged chiral solvating agents for the enantiodiscrimination of N-protected aminoalkanephosphonates – a comparative NMR study. Tetrahedron Asymmetry 20:2709–2714
Gorecki L, Berlicki L, Mucha A, Kafarski P, Slepokura K, Rudzinska-Szostak E (2012) Phosphorylation as a method of tuning the enantiodiscrimination potency of quinine – an NMR study. Chirality 24:318–328
Faigl F, Vas-Feldhoffer B, Kubinyi M, Pal K, Tarkanyi G, Czugler M (2009) Efficient synthesis of optically active 1-(2-carboxymethyl-6-ethylphenyl)-1H-pyrrole-2-carboxylic acid: a novel atropisomeric 1-arylpyrrole derivative. Tetrahedron Asymmetry 20:98–103
Kwon C, Yoo KM, Jung S (2009) Chiral separation and discrimination of catechin by sinorhizobial octasaccharides in capillary electrophoresis and 13C NMR spectroscopy. Carbohydr Res 344:1347–1351
D’Acquarica I, Gasparrini F, Misiti D, Pierini M, Villani C (2008) HPLC chiral stationary phases containing macrocyclic antibiotics: practical aspects and recognition mechanism. Adv Chromatogr 46:109–173
Uccello-Barretta G, Vanni L, Balzano F (2010) Nuclear magnetic resonance approaches to the rationalization of chromatographic enantiorecognition processes. J Chromatogr A 1217:928–940
Chankvetadze B, Blaschke G (1999) Selector-selectand interactions in chiral capillary electrophoresis. Electrophoresis 20:2592–2604
Chankvetadze B, Burjanadze N, Maynard DM, Bergander K, Bergenthal D, Blaschke G (2002) Comparative enantioseparations with native β-cyclodextrin and heptakis-(2-O-methyl-3,6-di-O-sulfo)-β-cyclodextrin in capillary electrophoresis. Electrophoresis 23:3027–3034
Chankvetadze B (2004) Combined approach using capillary electrophoresis and NMR spectroscopy for an understanding of enantioselective recognition mechanisms by cyclodextrins. Chem Soc Rev 33:337–347
Vega ED, Lomsadze K, Chankvetadze L, Salgado A, Scriba GKE, Calvo E, Lopez JA, Crego AL, Marina ML, Chankvetadze B (2011) Separation of enantiomers of ephedrine by capillary electrophoresis using cyclodextrins as chiral selectors: comparative CE, NMR and high resolution MS studies. Electrophoresis 32:2640–2647
Lomsadze K, Vega ED, Salgado A, Crego AL, Scriba GKE, Marina ML, Chankvetadze B (2012) Separation of enantiomers of norephedrine by capillary electrophoresis using cyclodextrins as chiral selectors: comparative CE and NMR studies. Electrophoresis 33:1637–1647
Schurig V (2012) Separation of enantiomers. In: Poole CF (ed) Gas chromatography. Elsevier, Oxford, pp 495–517
Schurig V (2011) Gas chromatographic enantioseparation of derivatized α-amino acids on chiral stationary phases – past and present. J Chromatogr B 879:3122–3140
Schurig V (2010) Use of derivatized cyclodextrins as chiral selectors for the separation of enantiomers by gas chromatography. Ann Pharm Fr 68:82–98
Wistuba D, Schurig V (2009) The separation of enantiomers on modified cyclodextrins by capillary electrochromatography (CEC). LC-GC Eur 22:60, 62–64, 66–69
Szejtli J (2004) Past, present, and future of cyclodextrin research. Pure Appl Chem 76:1825–1845
Dodziuk H (ed) (2008) Cyclodextrins and their complexes. Wiley-VCH, Weinheim
Loftsson T, Brewster ME (2012) Cyclodextrins as functional excipients: methods to enhance complexation efficiency. J Pharm Sci 101:3019–3032
Perez-Trujillo M, Lindon JC, Parella T, Keun HC, Nicholson JK, Athersuch TJ (2012) Chiral metabonomics: 1H NMR-based enantiospecific differentiation of metabolites in human urine via direct cosolvation with β-cyclodextrin. Anal Chem 84:2868–2874
Dodziuk H, Kozminski W, Ejchart A (2004) NMR studies of chiral recognition by cyclodextrins. Chirality 16:90–105
Schneider H-J, Hacket F, Ruediger V, Ikeda H (1998) NMR studies of cyclodextrins and cyclodextrin complexes. Chem Rev 98:1755–1785
Szejtli J (1998) Introduction and general overview of cyclodextrin chemistry. Chem Rev 98:1743–1753
Uccello-Barretta G, Balzano F, Cuzzola A, Menicagli R, Salvadori P (2000) NMR detection of the conformational distortion induced in cyclodextrins by introduction of alkyl or aromatic substituents. Eur J Org Chem 449–453
Uccello-Barretta G, Sicoli G, Balzano F, Salvadori P (2003) A conformational model of per-O-acetyl-cyclomaltoheptaose (-β-cyclodextrin) in solution: detection of partial inversion of glucopyranose units by NMR spectroscopy. Carbohydr Res 338:1103–1107
Uccello-Barretta G, Sicoli G, Balzano F, Salvadori P (2005) NMR spectroscopy: a powerful tool for detecting the conformational features of symmetrical per-substituted mixed cyclomaltoheptaoses (β-cyclodextrins). Carbohydr Res 340:271–281
Casy AF, Mercer AD (1988) Application of cyclodextrins to chiral analysis by proton NMR spectroscopy. Magn Reson Chem 26:765–774
Greatbanks D, Pickford R (1987) Cyclodextrins as chiral complexing agents in water, and their application to optical purity measurements. Magn Reson Chem 25:208–215
Blazewska KM, Ni F, Haiges R, Kashemirov BA, Coxon FP, Stewart CA, Baron R, Rogers MJ, Seabra MC, Ebetino FH, McKenna CE (2011) Synthesis, stereochemistry and SAR of a series of minodronate analogues as RGGT inhibitors. Eur J Med Chem 46:4820–4826
Redondo J, Capdevila A, Latorre I, Bertran J (2012) Host–guest complexation of omeprazole, pantoprazole and rabeprazole sodium salts with cyclodextrins: an NMR study on solution structures and enantiodiscrimination power. J Incl Phenom Macrocycl Chem 73:225–236
Esturau N, Espinosa JF (2006) Optimization of diffusion-filtered NMR experiments for selective suppression of residual nondeuterated solvent and water signals from 1H NMR spectra of organic compounds. J Org Chem 71:4103–4110
Lee Y-J, Choi S, Lee J, Nguyen NVT, Lee K, Kang JS, Mar W, Kim KH (2012) Chiral discrimination of sibutramine enantiomers by capillary electrophoresis and proton nuclear magnetic resonance spectroscopy. Arch Pharm Res 35:671–681
Molaabasi F, Talebpour Z (2011) Enantiomeric discrimination and quantification of the chiral organophosphorus pesticide fenamiphos in aqueous samples by a novel and selective 31P nuclear magnetic resonance spectroscopic method using cyclodextrins as chiral selector. J Agric Food Chem 59:803–808
Smith KJ, Wilcox JD, Mirick GE, Wacker LS, Ryan NS, Vensel DA, Readling R, Domush HL, Amonoo EP, Shariff SS, Wenzel TJ (2003) Calix[4]arene, calix[4]resorcarene, and cyclodextrin derivatives and their lanthanide complexes as chiral NMR shift reagents. Chirality 15:S150–S158
Wenzel TJ, Amonoo EP, Shariff SS, Aniagyei SE (2003) Sulfated and carboxymethylated cyclodextrins and their lanthanide complexes as chiral NMR discriminating agents. Tetrahedron Asymmetry 14:3099–3104
Dignam CF, Randall LA, Blacken RD, Cunningham PR, Lester S-KG, Brown MJ, French SC, Aniagyei SE, Wenzel TJ (2006) Carboxymethylated cyclodextrin derivatives as chiral NMR discriminating agents. Tetrahedron Asymmetry 17:1199–1208
Provencher KA, Weber MA, Randall LA, Cunningham PR, Dignam CF, Wenzel TJ (2010) Carboxymethylated cyclodextrins and their complexes with Pr(III) and Yb(III) as water-soluble chiral NMR solvating agents for cationic compounds. Chirality 22:336–346
Provencher KA, Wenzel TJ (2008) Carboxymethylated cyclodextrins and their paramagnetic lanthanide complexes as water-soluble chiral NMR solvating agents. Tetrahedron Asymmetry 19:1797–1803
Chisholm CD, Wenzel TJ (2011) Enantiomeric discrimination of aromatic-containing anionic substrates using cationic cyclodextrins. Tetrahedron Asymmetry 22:62–68
Rekharsky M, Yamamura H, Kawai M, Inoue Y (2001) Critical difference in chiral recognition of N-Cbz-d/l-aspartic and -glutamic acids by mono- and bis(trimethylammonio)-β-cyclodextrins. J Am Chem Soc 123:5360–5361
Park KK, Lim HS, Park JW (1999) Chiral discrimination of phenylacetic acid derivatives by xylylenediamine-modified β-cyclodextrins. Bull Korean Chem Soc 20:211–213
Sun P, MacDonnell FM, Armstrong DW (2009) Enantioselective host–guest complexation of Ru(II) trisdiimine complexes using neutral and anionic derivatized cyclodextrins. Inorg Chim Acta 362:3073–3078
Koehler JEH, Hohla M, Richters M, König WA (1992) Cyclodextrin derivatives as chiral selectors. Investigation of interaction with (R,S)-methyl 2-chloropropionate by enantioselective gas chromatography, NMR spectroscopy and molecular dynamics simulation. Angew Chem Int Ed Engl 31:319–320
Schmidt R, Roeder M, Oeckler O, Simon A, Schurig V (2000) Separation and absolute configuration of the enantiomers of a degradation product of the new inhalation anesthetic sevoflurane. Chirality 12:751–755
Sicoli G, Jiang Z, Jicsinsky L, Schurig V (2005) Modified linear dextrins (“acyclodextrins”) as new chiral selectors for the gas-chromatographic separation of enantiomers. Angew Chem Int Ed 44:4092–4095
Uccello-Barretta G, Sicoli G, Balzano F, Schurig V, Salvadori P (2006) Highly efficient NMR enantio-discrimination of 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane, a chiral degradation product of sevoflurane, by heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin. Tetrahedron Asymmetry 17:2504–2510
Uccello-Barretta G, Balzano F, Pertici F, Jicsinszky L, Sicoli G, Schurig V (2008) External vs. internal interactions in the enantio-discrimination of fluorinated α-amino acid derivatives by heptakis[2,3-di-O-acetyl-6-O-(tert-butyldimethylsilyl)]-β-cyclodextrin, a powerful chiral solvating agent for NMR spectroscopy. Eur J Org Chem 1855–1863
Uccello-Barretta G, Balzano F, Caporusso AM, Iodice A, Salvadori P (1995) Permethylated β-cyclodextrin as chiral solvating agent for the NMR assignment of the absolute configuration of chiral trisubstituted allenes. J Org Chem 60:2227–2231
Uccello-Barretta G, Balzano F, Caporusso AM, Salvadori P (1994) Direct determination of the enantiomeric purity of chiral trisubstituted allenes by using permethylated cyclodextrin as a chiral solvating agent. J Org Chem 59:836–839
Uccello-Barretta G, Balzano F, Menicagli R, Salvadori P (1996) NMR chiral analysis of aromatic hydrocarbons by using permethylated β-cyclodextrin as chiral solvating agent. J Org Chem 61:363–365
Uccello-Baretta G, Cuzzola A, Balzano F, Menicagli R, Salvadori P (1998) Benzoylated and benzylated cyclodextrins. A new class of chiral solvating agents for chiral recognition of 3,5-dinitrophenyl derivatives by 1H-NMR spectroscopy. Eur J Org Chem 2009–2012
Uccello-Barretta G, Cuzzola A, Balzano F, Menicagli R, Iuliano A, Salvadori P (1997) A new stereochemical model from NMR for benzoylated cyclodextrins, promising new chiral solvating agents for the chiral analysis of 3,5-dinitrophenyl derivatives. J Org Chem 62:827–835
Uccello-Barretta G, Ferri L, Balzano F, Salvadori P (2003) Partially versus exhaustively carbamoylated cyclodextrins: NMR investigation on enantiodiscriminating capabilities in solution. Eur J Org Chem 1741–1748
Yashima E, Yamada M, Yamamoto C, Nakashima M, Okamoto Y (1997) Chromatographic enantio-separation and chiral discrimination in NMR by trisphenylcarbamate derivatives of cellulose, amylose, oligosaccharides, and cyclodextrins. Enantiomer 2:225–240
Kubota T, Yamamoto C, Okamoto Y (2002) Chromatographic enantioseparation by cycloalkylcarbamate derivatives of cellulose and amylose. Chirality 14:372–376
Uccello-Barretta G, Balzano F, Sicoli G, Scarselli A, Salvadori P (2005) NMR enantio-discrimination of polar and apolar substrates by multifunctional cyclodextrins. Eur J Org Chem 5349–5355
Boger J, Corcoran RJ, Lehn JM (1978) Cyclodextrin chemistry. Selective modification of all primary hydroxyl groups of α- and β-cyclodextrins. Helv Chim Acta 61:2190–2218
Ema T, Ura N, Eguchi K, Ise Y, Sakai T (2011) Chiral porphyrin dimer with a macrocyclic cavity for intercalation of aromatic guests. Chem Commun 47:6090–6092
Ema T (2012) Synthetic macrocyclic receptors in chiral analysis and separation. J Incl Phenom Macrocycl Chem 74:41–55
Shirakawa S, Moriyama A, Shimizu S (2007) Design of a novel inherently chiral calix[4]arene for chiral molecular recognition. Org Lett 9:3117–3119
Shirakawa S, Moriyama A, Shimizu S (2008) Synthesis, optical resolution and enantiomeric recognition ability of novel, inherently chiral calix[4]arenes: trial application to asymmetric reactions as organocatalysts. Eur J Org Chem 5957–5964
Xia Y-X, Zhou H-H, Shi J, Li S-Z, Zhang M, Luo J, Xiang G-Y (2012) An inherently chiral calix[4]crown carboxylic acid in the 1,2-alternate conformation. J Incl Phenom Macrocycl Chem 74:277–284
Uccello-Barretta G, Berni M-G, Balzano F (2007) Enantiodiscrimination by inclusion phenomena inside a bis(ethyl lactate) p-tert-butylcalix[4]arene derivative. Tetrahedron Asymmetry 18:2565–2572
Durmaz M, Yilmaz M, Sirit A (2011) Synthesis of chiral calix[4]arenes bearing aminonaphthol moieties and their use in the enantiomeric recognition of carboxylic acids. Org Biomol Chem 9:571–580
Ben Sdira S, Felix CP, Giudicelli M-BA, Seigle-Ferrand PF, Perrin M, Lamartine RJ (2003) Synthesis and structure of lower rim C-linked N-tosyl peptidocalix[4]arenes. J Org Chem 68:6632–6638
Ben Sdira S, Baudry R, Felix CP, Giudicelli M-BA, Lamartine RJ (2004) Synthesis and structure of lower rim C-linked tetra-N-tosyl peptidocalix[4]arenes. Tetrahedron Lett 45:7801–7804
Bois J, Bonnamour I, Duchamp C, Parrot-Lopez H, Darbost U, Felix C (2009) Enantioselective recognition of amino acids by chiral peptido-calix[4]arenes and thiacalix[4]arenes. New J Chem 33:2128–2135
Lhotak P (2004) Chemistry of thiacalixarenes. Eur J Org Chem 1675–1692
Wenzel TJ (2013) Chiral derivatizing agents, macrocycles, metal complexes, and liquid crystals for enantiomer differentiation in NMR spectroscopy. Top Curr Chem. doi:10.1007/128_2013_433
Pham NH, Wenzel TJ (2012) A water-soluble calix[4]resorcinarene with l-pipecolinic acid groups as a chiral NMR solvating agent. Chirality 24:193–200
Pham NH, Wenzel TJ (2011) A water-soluble calix[4]resorcinarene with α-methyl-l-prolinylmethyl groups as a chiral NMR solvating agent. J Org Chem 76:986–989
O’Farrell CM, Chudomel JM, Collins JM, Dignam CF, Wenzel TJ (2008) Water-soluble calix[4]resorcinarenes with hydroxyproline groups as chiral NMR solvating agents. J Org Chem 73:2843–2851
O’Farrell CM, Hagan KA, Wenzel TJ (2009) Water-soluble calix[4]resorcinarenes as chiral NMR solvating agents for bicyclic aromatic compounds. Chirality 21:911–921
Pham NH, Wenzel TJ (2011) A sulfonated calix[4]resorcinarene with α-methyl-l-prolinylmethyl groups as a water-soluble chiral NMR solvating agent. Tetrahedron Asymmetry 22:641–647
Pham NH, Wenzel TJ (2011) A sulfonated calix[4]resorcinarene with l-pipecolinic acid groups as a water-soluble chiral NMR solvating agent. Tetrahedron Asymmetry 22:1574–1580
Hagan KA, O’Farrell CM, Wenzel TJ (2009) Water-soluble calix[4]resorcinarenes with hydroxyproline groups as chiral NMR solvating agents for phenyl- and pyridyl-containing compounds. Eur J Org Chem 4825–4832
O’Farrell CM, Wenzel TJ (2008) Water-soluble calix[4]resorcinarenes as chiral NMR solvating agents for phenyl-containing compounds. Tetrahedron Asymmetry 19:1790–1796
Wenzel TJ, Rollo RD, Clark RL (2012) Chiral discrimination of aliphatic amines and amino alcohols using NMR spectroscopy. Magn Reson Chem 50:261–265
Li N, Yang F, Stock HA, Dearden DV, Lamb JD, Harrison RG (2012) Resorcinarene-based cavitands with chiral amino acid substituents for chiral amine recognition. Org Biomol Chem 10:7392–7401
Amato ME, Ballistreri FP, D’Agata S, Pappalardo A, Tomaselli GA, Toscano RM, Sfrazzetto GT (2011) Enantioselective molecular recognition of chiral organic ammonium ions and amino acids using cavitand-salen-based receptors. Eur J Org Chem 5674–5680
Ema T, Tanida D, Sakai T (2006) Versatile and practical chiral shift reagent with hydrogen-bond donor/acceptor sites in a macrocyclic cavity. Org Lett 8:3773–3775
Ema T, Tanida D, Sakai T (2007) Versatile and practical macrocyclic reagent with multiple hydrogen-bonding sites for chiral discrimination in NMR. J Am Chem Soc 129:10591–10596
Ema T, Tanida D, Hamada K, Sakai T (2008) Tuning the chiral cavity of macrocyclic receptor for chiral recognition and discrimination. J Org Chem 73:9129–9132
Ema T, Tanida D, Sugita K, Sakai T, Miyazawa K, Ohnishi A (2008) Chiral selector with multiple hydrogen-bonding sites in a macrocyclic cavity. Org Lett 10:2365–2368
Ema T, Ura N, Eguchi K, Sakai T (2012) Molecular recognition of chiral diporphyrin receptor with a macrocyclic cavity for intercalation of aromatic compounds. Bull Chem Soc Jpn 85:101–109
Gasparrini F, Misiti D, Pierini M, Villani C (2002) A chiral A2B2 macrocyclic minireceptor with extreme enantioselectivity. Org Lett 4:3993–3996
Uccello-Barretta G, Balzano F, Martinelli J, Berni M-G, Villani C, Gasparrini F (2005) NMR enantiodiscrimination by cyclic tetraamidic chiral solvating agents. Tetrahedron Asymmetry 16:3746–3751
Uccello-Barretta G, Balzano F, Martinelli J, Gasparrini F, Pierini M, Villani C (2011) NMR and computational investigations of the chiral discrimination processes involving a cyclic tetraamidic chiral selector. Eur J Org Chem 3738–3747
Tanaka K, Nakai Y, Takahashi H (2011) Efficient NMR chiral discrimination of carboxylic acids using rhombamine macrocycles as chiral shift reagent. Tetrahedron Asymmetry 22:178–184
Periasamy M, Dalai M, Padmaja M (2010) Chiral trans-1,2-diaminocyclohexane derivatives as chiral solvating agents for carboxylic acids. J Chem Sci 122:561–569
Gualandi A, Grilli S, Savoia D, Kwit M, Gawronski J (2011) C-Hexaphenyl-substituted trianglamine as a chiral solvating agent for carboxylic acids. Org Biomol Chem 9:4234–4241
Ma F, Shen X, Ming X, Wang J, Ou-Yang J, Zhang C (2008) The novel macrocyclic compounds as chiral solvating agents for determination of enantiomeric excess of carboxylic acids. Tetrahedron Asymmetry 19:1576–1586
Ma F, Shen X, Ou-Yang J, Deng Z, Zhang C (2008) Macrocyclic compounds as chiral solvating agents for phosphinic, phosphonic, and phosphoric acids. Tetrahedron Asymmetry 19:31–37
Tanaka K, Fukuda N, Fujiwara T (2007) Trianglamine as a new chiral shift reagent for secondary alcohols. Tetrahedron Asymmetry 18:2657–2661
Tanaka K, Fukuda N (2009) “Calixarene-like” chiral amine macrocycles as novel chiral shift reagents for carboxylic acids. Tetrahedron Asymmetry 20:111–114
Quinn TP, Atwood PD, Tanski JM, Moore TF, Folmer-Andersen JF (2011) Aza-crown macrocycles as chiral solvating agents for mandelic acid derivatives. J Org Chem 76:10020–10030
Carrillo R, Lopez-Rodriguez M, Martin VS, Martin T (2009) Quantification of a CH-π interaction responsible for chiral discrimination and evaluation of its contribution to enantioselectivity. Angew Chem Int Ed 48:7803–7808
Busto E, Gonzalez-Alvarez A, Gotor-Fernandez V, Alfonso I, Gotor V (2010) Optically active macrocyclic hexaazapyridinophanes decorated at the periphery: synthesis and applications in the NMR enantiodiscrimination of carboxylic acids. Tetrahedron 66:6070–6077
Gonzalez-Alvarez A, Alfonso I, Gotor V (2006) An azamacrocyclic receptor as efficient polytopic chiral solvating agent for carboxylic acids. Tetrahedron Lett 47:6397–6400
Gospodarowicz K, Holynska M, Paluch M, Lisowski J (2012) Novel chiral hexaazamacrocycles for the enantiodiscrimination of carboxylic acids. Tetrahedron 68:9930–9935
Wenzel TJ, Thurston JE (2000) Enantiomeric discrimination in the NMR spectra of underivatized amino acids and α-methyl amino acids using (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. Tetrahedron Lett 41:3769–3772
Wenzel TJ, Thurston JE (2000) (+)-(18-Crown-6)-2,3,11,12-tetracarboxylic acid and its ytterbium(III) complex as chiral NMR discriminating agents. J Org Chem 65:1243–1248
Machida Y, Kagawa M, Nishi H (2003) Nuclear magnetic resonance studies for the chiral recognition of (+)-(R)-18-crown-6-tetracarboxylic acid to amino compounds. J Pharm Biomed Anal 30:1929–1942
Lee W, Bang E, Baek C-S, Lee W (2004) Chiral discrimination studies of (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid by high-performance liquid chromatography and NMR spectroscopy. Magn Reson Chem 42:389–395
Lovely AE, Wenzel TJ (2006) Chiral NMR discrimination of secondary amines using (18-crown-6)-2,3,11,12-tetracarboxylic acid. Org Lett 8:2823–2826
Chisholm CD, Fueloep F, Forro E, Wenzel TJ (2010) Enantiomeric discrimination of cyclic β-amino acids using (18-crown-6)-2,3,11,12-tetracarboxylic acid as a chiral NMR solvating agent. Tetrahedron Asymmetry 21:2289–2294
Lovely AE, Wenzel TJ (2008) Chiral NMR discrimination of amines: analysis of secondary, tertiary, and prochiral amines using (18-crown-6)-2,3,11,12-tetracarboxylic acid. Chirality 20:370–378
Koide T, Ueno K (2001) Mechanistic study of enantiomeric recognition of primary amino compounds using an achiral crown ether with cyclodextrin by capillary electrophoresis and nuclear magnetic resonance. J Chromatogr A 923:229–239
Wenzel TJ, Bourne CE, Clark RL (2009) (18-Crown-6)-2,3,11,12-tetracarboxylic acid as a chiral NMR solvating agent for determining the enantiomeric purity and absolute configuration of β-amino acids. Tetrahedron Asymmetry 20:2052–2060
Lovely AE, Wenzel TJ (2006) Chiral NMR discrimination of piperidines and piperazines using (18-crown-6)-2,3,11,12-tetracarboxylic acid. J Org Chem 71:9178–9182
Howard JA, Nonn M, Fulop F, Wenzel TJ (2013) Enantiomeric discrimination of isoxazoline fused β-amino acid derivatives using (18-crown-6)-2,3,11,12-tetracarboxylic acid as a chiral NMR solvating agent. Chirality 25:48–53
Bang E, Jin JY, Hong JH, Kang JS, Lee W, Lee W (2012) Comparative studies on enantiomer resolution of α-amino acids and their esters using (18-crown-6)-tetracarboxylic acid as a chiral crown ether selector by NMR spectroscopy and high-performance liquid chromatography. Bull Korean Chem Soc 33:3481–3484
Szumna A (2009) Chiral encapsulation by directional interactions. Chem Eur J 15:12381–12388
Wehner M, Schrader T, Finocchiaro P, Failla S, Consiglio G (2000) A chiral sensor for arginine and lysine. Org Lett 2:605–608
Consiglio GA, Failla S, Finocchiaro P (2008) New cleft-like molecules and macrocycles from phosphonate substituted spirobisindanol. Molecules 13:678–700
Holman KT (2004) Cryptophanes: molecular containers. In: Atwood JL, Steed JW (eds) Encyclopedia of supramolecular chemistry. CRC, New York, pp 340–348
Canceill J, Lacombe L, Collet A (1985) Analytical optical resolution of bromochlorofluoromethane by enantioselective inclusion into a tailor-made cryptophane and determination of its maximum rotation. J Am Chem Soc 107:6993–6996
Soulard P, Asselin P, Cuisset A, Aviles Moreno JR, Huet TR, Petitprez D, Demaison J, Freedman TB, Cao X, Nafie LA, Crassous J (2006) Chlorofluoroiodomethane as a potential candidate for parity violation measurements. Phys Chem Chem Phys 8:79–92
Bouchet A, Brotin T, Linares M, Aagren H, Cavagnat D, Buffeteau T (2011) Enantioselective complexation of chiral propylene oxide by an enantiopure water-soluble cryptophane. J Org Chem 76:4178–4181
Bouchet A, Brotin T, Linares M, Cavagnat D, Buffeteau T (2011) Influence of the chemical structure of water-soluble cryptophanes on their overall chiroptical and binding properties. J Org Chem 76:7816–7825
Petkovic M, Seddon KR, Rebelo LPN, Pereira CS (2011) Ionic liquids: a pathway to environmental acceptability. Chem Soc Rev 40:1383–1403
Sachnov SJ, Schneiders K, Schulz PS, Wasserscheid P (2010) Chirality transfer in mandelate ionic liquids through ion pairing effects. Tetrahedron Asymmetry 21:1821–1824
Bica K, Gaertner P (2008) Applications of chiral ionic liquids. Eur J Org Chem 3235–3250
Payagala T, Armstrong DW (2012) Chiral ionic liquids: a compendium of syntheses and applications (2005–2012). Chirality 24:17–53
Ding J, Welton T, Armstrong DW (2004) Chiral ionic liquids as stationary phases in gas chromatography. Anal Chem 76:6819–6822
Rizvi SAA, Shamsi SA (2006) Synthesis, characterization, and application of chiral ionic liquids and their polymers in micellar electrokinetic chromatography. Anal Chem 78:7061–7069
Yuan LM, Han Y, Zhou Y, Meng X, Li ZY, Zi M, Chang YX (2006) (R)-N,N,N-Trimethyl-2-aminobutanol-bis(trifluoromethane-sulfon)imidate chiral ionic liquid used as chiral selector in HPCE, HPLC, and CGC. Anal Lett 39:1439–1449
Wasserscheid P, Boesmann A, Bolm C (2002) Synthesis and properties of ionic liquids derived from the “chiral pool”. Chem Commun 200–201
Ishida Y, Miyauchi H, Saigo K (2002) Design and synthesis of a novel imidazolium-based ionic liquid with planar chirality. Chem Commun 2240–2241
Ishida Y, Sasaki D, Miyauchi H, Saigo K (2006) Synthesis and properties of a diastereopure ionic liquid with planar chirality. Tetrahedron Lett 47:7973–7976
Bwambok DK, Marwani HM, Fernand VE, Fakayode SO, Lowry M, Negulescu I, Strongin RM, Warner IM (2008) Synthesis and characterization of novel chiral ionic liquids and investigation of their enantiomeric recognition properties. Chirality 20:151–158
Bwambok DK, Challa SK, Lowry M, Warner IM (2010) Amino acid-based fluorescent chiral ionic liquid for enantiomeric recognition. Anal Chem 82:5028–5037
Gonzalez L, Altava B, Bolte M, Burguete MI, Garcia-Verdugo E, Luis SV (2012) Synthesis of chiral room temperature ionic liquids from amino acids – application in chiral molecular recognition. Eur J Org Chem 4996–5009
Altava B, Barbosa DS, Isabel Burguete M, Escorihuela J, Luis SV (2009) Synthesis of new chiral imidazolium salts derived from amino acids: their evaluation in chiral molecular recognition. Tetrahedron Asymmetry 20:999–1003
Tabassum S, Gilani MA, Wilhelm R (2011) Imidazolinium sulfonate and sulfamate zwitterions as chiral solvating agents for enantiomeric excess calculations. Tetrahedron Asymmetry 22:1632–1639
De Rooy SL, Li M, Bwambok DK, El-Zahab B, Challa S, Warner IM (2011) Ephedrinium-based protic chiral ionic liquids for enantiomeric recognition. Chirality 23:54–62
Winkel A, Wilhelm R (2010) New chiral ionic liquids based on enantiopure sulfate and sulfonate anions for chiral recognition. Eur J Org Chem 5817–5824
Kumar V, Pei C, Olsen CE, Schaeffer SJC, Parmar VS, Malhotra SV (2008) Novel carbohydrate-based chiral ammonium ionic liquids derived from isomannide. Tetrahedron Asymmetry 19:664–671
Yu S, Lindeman S, Tran CD (2008) Chiral ionic liquids: synthesis, properties, and enantiomeric recognition. J Org Chem 73:2576–2591
Li M, Gardella J, Bwambok DK, El-Zahab B, de Rooy S, Cole M, Lowry M, Warner IM (2009) Combinatorial approach to enantiomeric discrimination: synthesis and 19F NMR screening of a chiral ionic liquid-modified silane library. J Comb Chem 11:1105–1114
Folmer-Andersen JF, Kitamura M, Anslyn EV (2006) Pattern-based discrimination of enantiomeric and structurally similar amino acids: an optical mimic of the mammalian taste response. J Am Chem Soc 128:5652–5653
Zhu X, Jiang J, Lei X, Chen X (2012) Rapid determination of enantiomeric excess of protected amino acids by catalytic amounts of chiral reagent. Anal Methods 4:1920–1923
Prabhu UR, Suryaprakash N (2010) Selective homonuclear decoupling in 1H NMR: application to visualization of enantiomers in chiral aligning medium and simplified analyses of spectra in isotropic solutions. J Phys Chem A 114:5551–5557
Nath N, Kumari D, Suryaprakash N (2011) Application of selective F1 decoupled 1H NMR for enantiomer resolution and accurate measurement of enantiomeric excess at low chiral substrate/auxiliary concentration. Chem Phys Lett 508:149–154
Pirkle WH, Sikkenga DL (1975) Use of achiral shift reagents to indicate relative stabilities of diastereomeric solvates. J Org Chem 40:3430–3434
Shundo A, Labuta J, Hill JP, Ishihara S, Ariga K (2009) Nuclear magnetic resonance signaling of molecular chiral information using an achiral reagent. J Am Chem Soc 131:9494–9495
Labuta J, Ishihara S, Shundo A, Arai S, Takeoka S, Ariga K, Hill JP (2011) Chirality sensing by nonchiral porphines. Chem Eur J 17:3558–3561
Shoji Y, Tashiro K, Aida T (2006) Sensing of chiral fullerenes by a cyclic host with an asymmetrically distorted π-electronic component. J Am Chem Soc 128:10690–10691
Shoji Y, Tashiro K, Aida T (2008) Chirality sensing of fullerenes using cyclic hosts having a chiral N-substituted porphyrin: a remote substituent effect. Chirality 20:420–424
Hanna GM (2006) NMR regulatory analysis: enantiomeric purity determination for (R)-(−)-desoxyephedrine and antipode methamphetamine. Pharmazie 61:188–193
Casy AF (1967) Applications of nuclear magnetic resonance spectroscopy in medicinal and pharmaceutical chemistry. J Pharm Sci 56:1049–1063
Holzgrabe U (2010) Quantitative NMR spectroscopy in pharmaceutical applications. Prog Nucl Magn Reson Spectrosc 57:229–240
Rao RN, Ramachandra B, Santhakumar K (2012) Evaluation of (R)-(−)-α-methoxyphenylacetic acid as a chiral shift reagent for resolution and determination of R and S enantiomers of modafinil in bulk drugs and formulations by 1H NMR spectroscopy. Chirality 24:339–344
Nunez-Agueero C-J, Escobar-Llanos C-M, Diaz D, Jaime C, Garduno-Juarez R (2006) Chiral discrimination of ibuprofen isomers in β-cyclodextrin inclusion complexes: experimental (NMR) and theoretical (MD, MM/GBSA) studies. Tetrahedron 62:4162–4172
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Uccello-Barretta, G., Balzano, F. (2013). Chiral NMR Solvating Additives for Differentiation of Enantiomers. In: Schurig, V. (eds) Differentiation of Enantiomers II. Topics in Current Chemistry, vol 341. Springer, Cham. https://doi.org/10.1007/128_2013_445
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DOI: https://doi.org/10.1007/128_2013_445
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