Regular Article/Proceedings from the 20th International Symposium on Chirality, Geneva, Switzerland, 2008
NMR enantiodifferentiation of quaternary ammonium salts of Tröger base
Christophe Michon,
Maria-Héléna Gonçalves-Farbos,
Jérôme Lacour,
Christophe Michon
Department of Organic Chemistry, University of Geneva, CH-1211 Geneva 4, Switzerland
Search for more papers by this authorMaria-Héléna Gonçalves-Farbos
Department of Organic Chemistry, University of Geneva, CH-1211 Geneva 4, Switzerland
Search for more papers by this authorCorresponding Author
Jérôme Lacour
Department of Organic Chemistry, University of Geneva, CH-1211 Geneva 4, Switzerland
Département de Chimie Organique, Université de Genève, Quai Ernest Ansermet 30, CH-1211 Genève 4, SwitzerlandSearch for more papers by this authorChristophe Michon,
Maria-Héléna Gonçalves-Farbos,
Jérôme Lacour,
Christophe Michon
Department of Organic Chemistry, University of Geneva, CH-1211 Geneva 4, Switzerland
Search for more papers by this authorMaria-Héléna Gonçalves-Farbos
Department of Organic Chemistry, University of Geneva, CH-1211 Geneva 4, Switzerland
Search for more papers by this authorCorresponding Author
Jérôme Lacour
Department of Organic Chemistry, University of Geneva, CH-1211 Geneva 4, Switzerland
Département de Chimie Organique, Université de Genève, Quai Ernest Ansermet 30, CH-1211 Genève 4, SwitzerlandSearch for more papers by this authorAbstract
Hexacoordinated phosphorus BINPHAT anion 1 is an efficient NMR chiral solvating agent for quaternary ammonium cations (quats) derived from Tröger base leading to large separations of the proton signals of the enantiomers and even in polar solvent media such as CD3CN (ΔΔδ up to 0.12 ppm). Quite surprisingly, this efficacy in the NMR split efficiency is not translated into a supramolecular stereocontrol (Pfeiffer effect) of the cation configuration by the anion. Chirality 2009. © 2009 Wiley-Liss, Inc.
LITERATURE CITED
- 1 Maruoka K,Ooi T. Enantioselective amino acid synthesis by chiral phase-transfer catalysis. Chem Rev 2003; 103: 3013–3028.
- 2 Lygo B,Andrews BI. Asymmetric phase-transfer catalysis utilizing chiral quaternary ammonium salts: asymmetric alkylation of glycine imines. Acc Chem Res 2004; 37: 518–525.
- 3 O'Donnell MJ. The enantioselective synthesis of alpha-amino acids by phase-transfer catalysis with achiral schiff base esters. Acc Chem Res 2004; 37: 506–517.
- 4 Vachon J,Lacour J. Recent developments in enantioselective phase transfer catalysis using chiral ammonium salts. Chimia 2006; 60: 266–275.
- 5 Hashimoto T,Maruoka K. Recent development and application of chiral phase-transfer catalysts. Chem Rev 2007; 107: 5656–5682.
- 6 Sarfati M,Lesot P,Merlet D,Courtieu J. Theoretical and experimental aspects of enantiomeric differentiation using natural abundance multinuclear NMR spectroscopy in chiral polypeptide liquid crystals. Chem Commun 2000; 21: 2069–2081.
- 7 Uccello-Barretta G,Balzano F,Salvadori P. Enantiodiscrimination by NMR spectroscopy. Curr Pharm Des 2006; 12: 4023–4045.
- 8 Seco JM,Quinoa E,Riguera R. The assignment of absolute configuration by NMR. Chem Rev 2004; 104: 17–117.
- 9 Duddeck H. 77Se NMR spectroscopy and its applications in chemistry. Annu Rep NMR Spectrosc 2004; 52: 105–166.
- 10 Wenzel TJ,Wilcox JD. Chiral reagents for the determination of enantiomeric excess and absolute configuration using NMR spectroscopy. Chirality 2003; 15: 256–270.
- 11 Rothchild R. NMR methods for determination of enantiomeric excess. Enantiomer 2000; 5: 457–471.
- 12 Parker D. NMR determination of enantiomeric purity. Chem Rev 1991; 91: 1441–1457.
- 13 Pirkle WH,Hoover DJ. NMR chiral solvating agents. Top Stereochem 1982; 13: 263–331.
- 14 Lacour J,Londez A,Goujon-Ginglinger C,Buß V,Bernardinelli G. Configurational ordering of cationic chiral dyes using a novel C2-symmetric hexacoordinated phosphate anion. Org Lett 2000; 2: 4185–4188.
- 15 Lacour J,Frantz R. New chiral anion mediated asymmetric chemistry. Org Biomol Chem 2005; 3: 15–19.
- 16 Lacour J,Linder D. Hexacoordinated phosphates: how to teach old chiral anions new asymmetric tricks. Chem Rec 2007; 7: 275–285.
- 17 Govindaswamy P,Linder D,Lacour J,Suess-Fink G,Therrien B. Chiral or not chiral? a case study of the hexanuclear metalloprisms [Cp*6M6(micro 3-tpt-kN)2(micro-C2O4-kO)3]6+ (M = Rh, Ir, tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine). Dalton Trans 2007; 39: 4457–4463.
- 18 Zalubovskis R,Bouet A,Fjellander E,Constant S,Linder D,Fischer A,Lacour J,Privalov T,Moberg C. Self-adaptable catalysts: substrate-dependent ligand configuration. J Am Chem Soc 2008; 130: 1845–1855.
- 19 Hebbe V,Londez A,Goujon-Ginglinger C,Meyer F,Uziel J,Juge S,Lacour J. NMR enantiodifferentiation of triphenylphosphonium salts by chiral hexacoordinated phosphate anions. Tetrahedron Lett 2003; 44: 2467–2471.
- 20 Herse C,Bas D,Krebs FC,Buergi T,Weber J,Wesolowski T,Laursen BW,Lacour J. A highly configurationally stable [4]heterohelicenium cation. Angew Chem Int Ed 2003; 42: 3162–3166.
- 21 Laleu B,Bernardinelli G,Chauvin R,Lacour J. Trimesitylmethylphosphonium cation. Supramolecular stereocontrol and simple enantiomerization mechanism determination. J Org Chem 2006; 71: 7412–7416.
- 22 Liu Y,Bonvallet PA,Vignon SA,Khan SI,Stoddart JF. Donor-acceptor pretzelanes and a cyclic bis[2]catenane homologue. Angew Chem Int Ed 2005; 44: 3050–3055.
- 23 Martinez-Viviente E,Pregosin PS,Vial L,Herse C,Lacour J. 1H, 19F, and 31P PGSE NMR diffusion studies on chiral organic salts: ion pairing and the dependence of a diffusion value on diastereomeric structure. Chem Eur J 2004; 10: 2912–2918.
- 24 Pasquato L,Herse C,Lacour J. NMR enantiodifferentiation of thiiranium cations by chiral hexacoordinated phosphate anions. Tetrahedron Lett 2002; 43: 5517–5520.
- 25 Pasquini C,Desvergnes-Breuil V,Jodry JJ,Dalla Cort A,Lacour J. Chiral anion-mediated asymmetric induction onto chiral diquats. Tetrahedron Lett 2002; 43: 423–426.
- 26 Vignon SA,Wong J,Tseng H-R,Stoddart JF. Helical chirality in donor-acceptor catenanes. Org Lett 2004; 6: 1095–1098.
- 27 Lacour J,Ginglinger C,Grivet C,Bernardinelli G. Synthesis and resolution of the configurationally stable tris(tetrachlorobenzenediolato)phosphate anion. Angew Chem Int Ed Engl 1997; 36: 608–609.
- 28 Heinrichs G,Kubik S,Lacour J,Vial L. Matched/mismatched interaction of a cyclic hexapeptide with ion pairs containing chiral cations and chiral anions. J Org Chem 2005; 70: 4498–4501.
- 29 Favarger F,Goujon-Ginglinger C,Monchaud D,Lacour J. Large scale synthesis and resolution of TRISPHAT [tris(tetrachlorobenzenediolato) phosphate(V)] Anion. J Org Chem 2004; 69: 8521–8524.
- 30 Ginglinger C,Jeannerat D,Lacour J,Jugé S,Uziel J. 1H and 31P NMR determination of the enantiomeric purity of quaternary phosphonium cations using TRISPHAT as chiral shift agent. Tetrahedron Lett 1998; 39: 7495–7498.
- 31 Lacour J,Vial L,Herse C. Efficient NMR enantiodifferentiation of chiral quats with BINPHAT anion. Org Lett 2002; 4: 1351–1354.
- 32 Gonçalves-Farbos M-H,Vial L,Lacour J. Enantioselective [1,2]-Stevens rearrangement of quaternary ammonium salts. A mechanistic evaluation. Chem Commun 2008; 7: 829–831.
- 33 Vial L,Gonçalves M-H,Morgantini P-Y,Weber J,Bernardinelli G,Lacour J. Unusual regio- and enantioselective [1,2]-Stevens rearrangement of a spirobi[dibenzazepinium] cation. Synlett 2004; 9: 1565–1568.
- 34 Vial L,Lacour J. Conformational preference and configurational control of highly symmetric spirobi[dibenzazepinium] cation. Org Lett 2002; 4: 3939–3942.
- 35 O'Farrell CM,Chudomel JM,Collins JM,Dignam CF,Wenzel TJ. Water-soluble calix[4]resorcinarenes with hydroxyproline groups as chiral NMR solvating agents. J Org Chem 2008; 73: 2843–2851.
- 36 Dignam CF,Zopf JJ,Richards CJ,Wenzel TJ. Water-soluble calix[4]resorcarenes as enantioselective NMR shift reagents for aromatic compounds. J Org Chem 2005; 70: 8071–8078.
- 37 Bergman SD,Frantz R,Gut D,Kol M,Lacour J. Effective chiral recognition among ions in polar medium. Chem Commun 2006: 850–852.
- 38 Kostyanovsky RG,Kostyanovsky VR,Kadorkina GK,Lyssenko KA. Wedekind-fock-havinga salt Me(Et)N+(All)PhI-center dot CHCl3 as historically the first object for absolute asymmetric synthesis: spontaneous resolution, structure and absolute configuration. Mendeleev Commun 2001(1): 1–5.
- 39
Tröger J.
Ueber einige mittelst nascirenden formaldehydes entstehende Basen.
J Prakt Chem
1887;
36:
225–245.
10.1002/prac.18870360123 Google Scholar
- 40 Prelog V,Wieland P. The resolution of Tröger's base into its optical antipodes, a note on the stereochemistry of trivalent nitrogen. Helv Chim Acta 1944; 27: 1127–1134.
- 41 Didier D,Sergeyev S. Analogues of Troger's base: recent developments and controversies. Targets Heterocycl Syst 2007; 11: 258–283.
- 42 Dolensky B,Elguero J,Kral V,Pardo C,Valik M. Current Troger's base chemistry. Adv Heterocycl Chem 2007; 93: 1–56.
- 43 Demeunynck M,Tatibouet A. Recent developments in Troger's base chemistry. Prog Heterocycl Chem 1999; 11: 1–20.
- 44 Pardo C,Alkorta I,Elguero J. A DFT study of the geometric, magnetic NMR chemical shifts and optical rotation properties of Troeger's bases. Tetrahedron: Asymmetry 2006; 17: 191–198.
- 45 Galasso V,Jones D,Modelli A. Molecular and electronic structure of Troger's bases. Chem Phys 2003; 288: 33–42.
- 46 Aamouche A,Devlin FJ,Stephens PJ. Structure, vibrational absorption and circular dichroism spectra, and absolute configuration of Troger's base. J Am Chem Soc 2000; 122: 2346–2354.
- 47 Wilen SH,Qi JZ,Williard PG. Resolution, asymmetric transformation, and configuration of Troeger's base. Application of Troeger's base as a chiral solvating agent. J Org Chem 1991; 56: 485–487.
- 48 Miller TR,Wagner EC. Some analogs of Troeger's base and related compounds. J Am Chem Soc 1941; 63: 832–836.
- 49 Spielman MA. The structure of Troeger's base. J Am Chem Soc 1935; 57: 583–585.
- 50 Faroughi M,Try AC,Klepetko J,Turner P. Changing the shape of Troger's base. Tetrahedron Lett 2007; 48: 6548–6551.
- 51 Didier D,Sergeyev S. Bromination and iodination of 6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine: a convenient entry to unsymmetrical analogs of Troeger's base. Eur J Org Chem 2007; 23: 3905–3910.
- 52 Satishkumar S,Periasamy M. A convenient method for the synthesis and resolution of Troeger base. Tetrahedron: Asymmetry 2006; 17: 1116–1119.
- 53 Ishida Y,Ito H,Mori D,Saigo K. Regio/diastereo-controls of the Bingel-type biscyclopropanation of [60]fullerene by using bismalonates with a Troeger base analogue-derived tether. Tetrahedron Lett 2005; 46: 109–112.
- 54 Sergeyev S,Diederich F. Regio- and stereoselective tether-directed remote functionalization of C60 with derivatives of the Troger base. Angew Chem Int Ed 2004; 43: 1738–1740.
- 55 Jensen J,Strozyk M,Warnmark K. Influence of scale, stoichiometry and temperature on the synthesis of 2,8-dihalo analogs of Troger's base from the corresponding anilines and paraformaldehyde. J Heterocycl Chem 2003; 40: 373–375.
- 56 Harmata M,Kahraman M. Congeners of Troeger's base as chiral ligands. Tetrahedron: Asymmetry 2000; 11: 2875–2879.
- 57 Miyahara Y,Izumi K,Ibrahim AA,Inazu T. Novel C2 chiral diamine ligands derived from cyclic Troger bases. Tetrahedron Lett 1999; 40: 1705–1708.
- 58 Crossley MJ,Try AC,Walton R. Synthesis of accurate distance models of the primary donor—primary acceptor pair of bacterial photosynthetic reaction centers. Tetrahedron Lett 1996; 37: 6807–6810.
- 59 Valik M,Cejka J,Havlik M,Kral V,Dolensky B. Calix-Tris-Troger's bases—a new cavitand family. Chem Commun 2007; 37: 3835–3837.
- 60 Kim EI,Paliwal S,Wilcox CS. Measurements of molecular electrostatic field effects in edge-to-face aromatic interactions and CH-pi interactions with implications for protein folding and molecular recognition. J Am Chem Soc 1998; 120: 11192–11193.
- 61 Crossley MJ,Mackay LG,Try AC. Enantioselective recognition of histidine and lysine esters by porphyrin chiral clefts and detection of amino-acid conformations in the bound-state. J Chem Soc Chem Commun 1995; 18: 1925–1927.
- 62 Tatibouët A,Demeunynck M,Andraud C,Collet A,Lhomme J. Synthesis and study of an acridine substituted Troger's base: preferential binding of the (-)-isomer to B-DNA. Chem Commun 1999; 2: 161–162.
- 63 Wilcox CS,Cowart MD. New approaches to synthetic receptors—synthesis and host properties of a water-soluble macrocyclic analog of Troger base. Tetrahedron Lett 1986; 27: 5563–5566.
- 64 Kiehne U,Bruhn T,Schnakenburg G,Frohlich R,Bringmann G,Lützen A. Synthesis, resolution, and absolute configuration of difunctionalized Troger's base derivatives. Chem Eur J 2008; 14: 4246–4255.
- 65 Khoshbin MS,Ovchinnikov MV,Mirkin CA,Golen JA,Rheingold AL. Metallomacrocycles incorporating a hemilabile Troeger's base derived ligand. Inorg Chem 2006; 45: 2603–2609.
- 66 Didier D,Tylleman B,Lambert N,Velde CMLV,Blockhuys F,Collas A,Sergeyev S. Functionalized analogues of Troger's base: scope and limitations of a general synthetic procedure and facile, predictable method for the separation of enantiomers. Tetrahedron 2008; 64: 6252–6262.
- 67 Zhong Q,He L,Beesley TE,Trahanovsky WS,Sun P,Wang C,Armstrong DW. Development of dinitrophenylated cyclodextrin derivatives for enhanced enantiomeric separations by high-performance liquid chromatography. J Chromatogr A 2006; 1115: 19–45.
- 68 Sajonz P,Gong X,Leonard WRJr,Biba M,Welch CJ. Multiparallel chiral method development screening using an 8-channel microfluidic HPLC system. Chirality 2006; 18: 803–813.
- 69 Yamamoto C,Yashima E,Okamoto Y. Structural analysis of amylose Tris(3,5-dimethylphenylcarbamate) by NMR relevant to its chiral recognition mechanism in HPLC. J Am Chem Soc 2002; 124: 12583–12589.
- 70 Tobler E,Lammerhofer M,Wuggenig F,Hammerschmidt F,Lindner W. Low-molecular-weight chiral cation exchangers: novel chiral stationary phases and their application for enantioseparation of chiral bases by nonaqueous capillary electrochromatography. Electrophoresis 2002; 23: 462–476.
- 71 Trapp O,Schurig V. Stereointegrity of Troeger's base: gas-chromatographic determination of the enantiomerization barrier. J Am Chem Soc 2000; 122: 1424–1430.
- 72 Jung M,Boernsen KO,Francotte E. Dextrin sulfopropyl ether: a novel anionic chiral buffer additive for enantiomer separation by electrokinetic chromatography. Electrophoresis 1996; 17: 130–136.
- 73 Lenev DA,Lyssenko KA,Golovanov DG,Buss V,Kostyanovsky RG. Bis-ortho-substitution by methyl groups dramatically increases theracemization barrier of Troger bases. Chem Eur J 2006; 12: 6412–6418.
- 74
Trapp O,Trapp G,Kong JW,Hahn U,Vögtle F,Schurig V.
Probing the stereointegrity of Troger's base—a dynamic electrokinetic chromatographic study.
Chem Eur J
2002;
8:
3629–3634.
10.1002/1521-3765(20020816)8:16<3629::AID-CHEM3629>3.0.CO;2-8 CAS PubMed Web of Science® Google Scholar
- 75 Lenev DA,Golovanov DG,Lyssenko KA,Kostyanovsky RG. Asymmetric nitrogen. Part 98. Configurationally stable methylates of methano- and ethano-Troger bases. Tetrahedron: Asymmetry 2006; 17: 2191–2194.
- 76 Häring M. Preparation of 5,11-endomethylenetetrahydrophenhomazines and 5-alkyltetrahydrophenhomazines. Helv Chim Acta 1963; 46: 2970–2982.
- 77
Monchaud D,Jodry JJ,Pomeranc D,Heitz V,Chambron J-C,Sauvage J-P,Lacour J.
Ion-pair mediated asymmetric synthesis of a configurationally stable mononuclear tris(diimine) iron(II) complex.
Angew Chem Int Ed
2002;
41:
2317–2319.
10.1002/1521-3773(20020703)41:13<2317::AID-ANIE2317>3.0.CO;2-W CAS PubMed Web of Science® Google Scholar
- 78 Monchaud D,Lacour J,Coudret C,Fraysse S. TRISPHAT salts. Efficient NMR chiral shift and resolving agents for substituted cyclometallated ruthenium bis(diimine) complexes. J Organomet Chem 2001; 624: 388–391.
- 79 Lacour J,Barchéchath S,Jodry JJ,Ginglinger C. Simple ion exchange procedure of common anions to TRISPHAT. Application to the purification of cationic species. Tetrahedron Lett 1998; 39: 567–570.
- 80 Weber E,Mueller U,Worsch D,Voegtle F,Will G,Kirfel A. Quaternary Troeger bases as new inclusion hosts: the first x-ray structures of a Troeger base and of a dioxane clathrate. J Chem Soc Chem Commun 1985; 22: 1578–1580.
- 81 Pfeiffer P,Quehl K. Uber einen neuen Effekt in Lösungen optisch-aktiver Substanzen. Chem Ber 1931; 64: 2667–2671.
- 82 Norden B,Tjerneld F. Binding of inert metal complexes to deoxyribonucleic acid detected by linear dichroism. FEBS Lett 1976; 67: 368–370.
- 83 Kirschner S,Ahmad N,Munir C,Pollock RJ. The Pfeiffer effect, outer-sphere complexation, and the absolute configuration of dissymmetric coordination compounds. Pure Appl Chem 1979; 51: 913–923.
- 84 Green MM,Khatri C,Peterson NC. A macromolecular conformational change driven by a minute chiral solvation energy. J Am Chem Soc 1993; 115: 4941–4942.
- 85 Yeh RM,Ziegler M,Johnson DW,Terpin AJ,Raymond KN. Imposition of chirality in a dinuclear triple-stranded helicate by ion pair formation. Inorg Chem 2001; 40: 2216–2217.
- 86 Lacour J,Jodry JJ,Monchaud D. Configurational ordering of a cationic dinuclear triple helicate by chiral TRISPHAT anions. Chem Commun 2001: 2302–2303.
- 87 Bonnot C,Chambron J-C,Espinosa E. Simultaneous freezing of chirality and in-out conformation of a macropentacyclic cryptand by protonation. J Am Chem Soc 2004; 126: 11412–11413.
- 88 Yeh RM,Raymond KN. Supramolecular asymmetric induction in dinuclear triple-stranded helicates. Inorg Chem 2006; 45: 1130–1139.
- 89
Lacour J,Jodry JJ,Ginglinger C,Torche-Haldimann S.
Diastereoselective Ion pairing of TRISPHAT anions and tris(4,4′-dimethyl-bipyridine)iron(II) Complex.
Angew Chem Int Ed Engl
1998;
37:
2379–2380.
10.1002/(SICI)1521-3773(19980918)37:17<2379::AID-ANIE2379>3.0.CO;2-C CAS Web of Science® Google Scholar
- 90 Pérollier C,Bernardinelli G,Lacour J. Sugar derived hexacoordinated phosphates: chiral anionic auxiliaries with general asymmetric efficiency. Chirality 2008; 20: 313–324.
- 91
Patonay T,Juhász-Tóth E,Bényei A.
Base-induced coupling of alpha-azido ketones with aldehydes—an easy and efficient route to trifunctionalized synthons 2-azido-3-hydroxy ketones, 2-acylaziridines, and 2-acylspiroaziridines.
Eur J Org Chem
2002;
2:
285–295.
10.1002/1099-0690(20021)2002:2<285::AID-EJOC285>3.0.CO;2-J Google Scholar
