DISCRIMINATION O FCHIRAL COMPOUNDSUSING NMRSPECTROSCOPY

THOMAS J. WENZEL

Preface

xxi

Acknowledgments

xxii i

1. Introduction

1

1 .1 . Chiral Derivatizing Agents

11 .2 . Chiral Solvating Agents

21 .3 . Overview of Chiral Reagents and Methodologies

41 .4 . Future Prospects

6

2. Aryl-Containing Carboxylic Acids

8

2 .1 . Introduction

82 .2 . a-Methoxy-a-trifluoromethylphenylacetic Acid

(MTPA-Mosher's Reagent)

1 12 .2 .1 . Analysis of Secondary Alcohols

1 32.2 .2 . Analysis of Secondary Diols and PoIyols

1 92.2 .3 . Analysis of Primary Alcohols

252 .2 .4 . Analysis of Tertiary Alcohols

2 62 .2 .5 . Analysis of Secondary Amines

2 62 .2 .6 . Analysis of Primary Amines

2 82 .2 .7. Use as a Chiral Solvating Agent

2 92 .2 .8 . Use of MTPA Derivatives with Paramagneti c

Lanthanide Chelates

3 02 .2 .9 . Use of MTPA Derivatives with Diamagnetic

Lanthanide Chelates

34

2 .2 .10 . Preparation of MTPA Derivatives

3 52 .2 .11 . Liquid Chromatography-NMR Spectroscop y

of MTPA Derivatives

3 52 .2 .12 . Database Methods with MTPA

3 52 .3 . a-Methoxyphenylacetic Acid (0-methyl Mandelic Acid-MPA)

3 82 .3 .1 . Analysis of Secondary Alcohols

3 92 .3 .2 . Analysis of Diols

422 .3 .3 . Analysis of Primary Alcohols

4 32 .3 .4 . Analysis of Amines

4 42 .3 .5 . Analysis of Sulfoxides

4 52 .3 .6 . Variable-temperature Method for Assignin g

Absolute Stereochemistry

4 62 .2 .7 . Barium(II) Method for Assignin g

Absolute Stereochemistry

472 .3 .8 . Use of MPA Derivatives with Lanthanide Chelates

4 82 .3 .9 . Use as a Chiral Solvating Agent

4 92 .3 .10 . Preparation of MPA Derivatives-The

"Mix and Shake" Method

5 02 .4 . Mandelic Acid (2-Hydroxy-2-phenyl Acetic Acid) (MA)

5 12 .5 . 0-Acetyl Mandelic Acid (2-Acetoxy-2-pheny l

Acetic Acid) (0-AMA)

5 32 .6 . Tetrahydropyranyl-protected Mandelic Acid [(2R)-2-phenyl-2 -

[(2S)-tetrahydro-2-pyranyloxy] Ethanoic Acid]

5 62 .7 . 0-Nitromandelic Acid

562 .8 . 2-Phenylpropionic Acid (2-PPA)

572 .9 . 2-Methoxy-2-phenylpropionic Acid

5 82 .10. 3-Phenylbutanoic Acid (3-PBA)/2-Phenylbutanoi c

Acid (2-PBA)

582 .11 . a-Methyl-a-methoxy(pentafluorophenyl) (Acetic Acid)

602 .12 . a-Cyano-a-fluorophenylacetic Acid

(CFPA)/a-Cyano-a-fluoronaphthylacetic Acid(CFNA)/a-Cyano-a-fluoro-p-tolylacetic Acid (CFTA)

602 .13 . N-Boc Phenylglycine (BPG)

6 22 .14 . 1,5-Difluoro-2,4-dinitrobenzene and Derivatives

6 32 .14.1 . N-(5-Fluoro-2,4-dinitrophenyl)-1-phenylethylamide

6 42 .14 .2 . 1-Fluoro-2,4-dinitrophenyl-5-(S)-alanine Amid e

(Marfey's Reagent)

6 52 .15 . 2-Fluoro-2-phenylacetic Acid/2-Fluoro-2-(1-naphthyl)propionic

Acid/2-Fluoro-2-(2-naphthyl)propionic Acid

6 62 .16 . a-Methoxy-a-(1-naphthyl) Acetic Aci d

(1-NMA)/a-Methoxy-a-(2-naphthyl) Acetic Acid (2-NMA)

6 72 .17 . 2-(1-Naphthyl)-2-phenylacetic Acid

7 02 .18 . 2-Methoxy-2-(1-naphthyl) Propionic Acid (MaNP)

7 12 .19 . 1-Methoxy-2,3-dihydro-1 H-cyclopenta[a]naphthalene -

1-carboxylic Acid

72

2 .20 . O-Aryl Lactic Acids

7 22 .21 . a-(2-Anthryl)-a-methoxyacetic Aci d

(2-AMA)/a-(9-Anthryl)-a-methoxyacetic Acid (9-AMA)

742 .22 . (a-[1-(9-Anthryl)]-2,2,2-trifluoroethoxy)acetic Acid

7 82 .23 . 2-Methoxy-2-(9-phenanthryl)propionic Acid

7 82 .24 . Summary

7 92 .24 .1 . Analysis of Primary Alcohols

7 92 .24 .2 . Analysis of Secondary Alcohols

7 92 .24.3 . Analysis of Tertiary Alcohols

8 02 .24 .4 . Analysis of Primary Amines

8 02 .24 .5 . Analysis of Secondary Amines

8 1

3 . Other Carboxylic Acid-based Reagents

8 2

3 .1 . Camphanic Acid

8 23 .2 . Menthoxyacetic Acid (MAA)

863 .3 . 2-(2,3-Anthracenedicarboximido)cyclohexan e

Carboxylic Acid

873 .4 . 313-Acetoxy-L5-etiocholenic Acid

8 83 .5 . Naproxen

8 93 .6 . 2-tert-Butyl-2-methyl- 1,3-benzodioxole-4-carboxylic Acid

9 03 .7 . endo-3-Benzamidonorbornane-2-carboxylic Acid

9 03 .8 . Coumarin-based Reagents

9 13 .9 . 2,2-Diphenylcyclopropane Carboxylic Acid

9 13 .10 . Amide Derivatives of Kemp's Triacid

9 13 .11 . Amino Acids

9 23 .11 .1 . N-Boc-phenylalanine

9 23 .11 .2 . Isotopically Substituted Amino Acids

9 23 .12 . (R)-(-)-(2,3,5,7-Tetranitro-9-fluorenyloximino)propanoic Acid

9 33 .13 . 2-Chloropropanoic Acid (2-CI-PA)

9 33 .14. Chlorofluoroacetic Acid

943 .15 . Perfluoropropoxy Propionic Acid/Perfluoro

Isopropropoxy Propionic Acid

943 .16 . 2-Methylbutyric Acid

943.17 . Lactic Acid and Derivatives

953 .17 .1 . Trifluorolactic Acid

95

3 .17 .2 . (S)-O-Acetyllactylchloride

9 5

3 .18 . Lasalocid

963 .19 . Axial Chiral Carboxylic Acids

9 63 .19 .1 . (+)-1-[2-Carboxy-6-(trifluoromethyl)phenyl]pyrrole-

2-carboxylic Acid

9 6

3 .19 .2 . 2'-Methoxy-1,1 '-binaphthyl-2-carboxylic Acid (MBNC)

9 7

3 .19.3 . 2'-Methoxy-1,1'-binaphthalene-8-carboxylic Acid

9 83 .19 .4 . 2'-Octylcarbamoyl-1,1 ' -binaphthyl-2-dicarboxylic Acid

10 0

3 .19 .5 . 2-(2'-Methoxy-1'-naphthyl)-3,5-dichlorobenzoi c

Acid (MNCB)

100

4. Hydroxyl- and Thiol-Containing Reagents

102

4.1 . 2,2,2-Trifluorophenylethanol (TFPE)

1034 .2 . 2,2,2-Trifluoro- 1 -(9 -anthryl)ethano l

(Pirkle's Alcohol (TFAE)

1094.2 .1 . Analysis of Sulfoxides

1094.2 .2 . Analysis of Lactones

1104 .2 .3 . Analysis of Lactams

11 14 .2 .4 . Analysis of Oxaziridines

1124 .2 .5 . Analysis of Axial Chiral Compounds

1124 .2 .6 . Analysis of Compounds that are Chiral by

Virtue of Slow Rotation

11 34 .2 .7 . Analysis of Metal Complexes

11 54 .2 .8 . Analysis of Cyclophosphazenes

11 64 .2 .9 . Analysis of Phosphine Oxides

11 74 .2 .10 . Analysis of Calixarenes

11 84 .2 .11 . Analysis of Other Substrates

1194 .2 .12 . Use of Lanthanide Chelates with TFPE and TFAE

1224 .2 .13 . Use as a Chiral Derivatizing Agent

1234 .3 . Other Anthryl-based Reagents

1234 .3 .1 . Analogs of TFAE

1234 .3 .2 . Ethyl-2-(9-anthryl)-2-hydroxyacetate

1264 .3 .3 . 2-(2,3-Anthracenedicarboximido)-1-cyclohexanol

12 74 .4 . 2,2,2-Trifluoro- 1 -( 1 -pyren yl)ethanol

1274 .5 . 2-(Trifluoromethyl)benzhydrol

1274 .6 . 1-Phenylethanol

12 84 .7. Methyl Mandelate (MM)

12 94 .8. Octahydro-8,9,9-trimethyl-5,8-methano-2H-1 -

benzopuran-2-ol (Noe's Reagent)

1304 .9. Menthol

1324 .10 . Borneol

13 54 .11 . (-)-10-Mercaptoisoborneol

13 54 .12 . (R)-(-)-Pantolactone

13 64 .13 . trans-Bis(hydroxydiphenylmethyl)-

2,2-dimethyl-1,3-dioxacyclopentane

13 64 .14 . 2-Hydroxymethyl-4,6-dimethyl-2-phenyl-1,3-dioxane

13 74 .15 . 2-Butanol

13 74 .16 . Assignment of Absolute Configuratio n

Using Glycosidation Shifts

13 84 .16 .1 . Analysis of Di- and Polysaccharides

14 14 .16 .2 . ß-n- and ß-L-Fucofuranoside/Arabinofuranoside

14 24 .17 . Linear Dextrins

14 44 .18 . Axial Chiral (Atropoisomeric) Alcohols

14 44 .18 .1 . 2,2' -Dihydroxy-1,1 ' -binaphthalene (BINOL)

14 54 .18 .2 . 8,8 ' -Dihydroxy-1,1'-binaphthalene

147

4 .18 .3 . Alkyl-Substituted Binaphthols

1474 .18 .4 . 2 ' -Hydroxy-1,1 ' -binaphthyl-2-yl[(3,5-dinitrobenzoyl )

amino](phenyl)acetate

1484 .18 .5 . 1,6-Di(o-chlorophenyl)-1,6-diphenylhexa -

2,4-diyne-1,6-di of

14 84 .18 .6 . 4,4 ' 6,6' -Tetrachloro-2,2 ' -bis(hydroxydiphenylmethyl )

biphenyl

14 84 .19 . Diol and Dithiol Reagents

1494.19 .1 . Butane-2,3-diol/Butane-2,3-thiol

1494.19 .2 . 2,2-Dimethyl-1,3-propanediol

15 04.19 .3 . 1,1,2-Triphenyl-1,2-ethanediol

15 14 .19 .4 . Ethylene Dithiol

15 14 .19 .5 . a,a,a' ,a' -Tetraphenyl-l,3-dioxolane-4,5-dimethanols )

(TADDOL)

15 1

5. Amine-based Reagents

153

5 .1 . Primary Amines

1545 .1 .1 . 1-Phenylethylamine (PEA)/1 -(1 -Naphthyl)ethylamin e

(NEA)/1 -(9-An thryl)ethylamine (AEA)

15 45 .1 .2 . Fluorinated Aryl Amines

16 15 .1 .3 . 9-(1-Amino-2,2-dimethylpropyl)-9,10-

dihydroanthracene

16 15 .1 .4 . (1S,2S)-1-Phenyl-2-amino-3-methoxy-l-propanol

16 25 .1 .5 . Phenylglycinol

16 35 .1 .6 . 1-(3-Aminopropyl)-(5R,8S,10R)terguride

16 35 .1 .7 . 5-Amino-4-aryl-2,2-dimethyl-1,3-dioxans

1645 .1 .8 . Amino Acids

1645 .1 .8 .1 . Peptides

1645 .1 .8 .2. Phenylglycine methyl ester (PGME) /

Phenylglycine dimethyl-amide

1655 .1 .8 .3 . L-Cysteine

1685 .1 .8 .4 . L-Proline

1695 .1 .9 . (IR,2R)-1-(1',8'-Naphthalimide)-2-aminocyclohexane

Derivatives

16 95 .1 .10 . 1-(1-Naphthyl)-2,2-dimethylpropylamine

17 05 .1 .11 . 1-Methoxy-2-aminopropane

17 05 .1 .12 . (+)-2-Amino-l-methoxymenth-8-ene

17 15 .2 . Secondary Amines

17 1

5 .2 .1 . Ephedrine

17 15 .2 .2 . 2-Methyl Piperidine

17 35 .2 .3 . (N-Methyl)-a-isosparteinium cation

1745 .2 .4 . N-Boc-1-(1-naphthyl)ethylamine

174

5 .2 .5 . N-Methyl-D-(-)-glucamine

17 5

5 .2 .6 . (S)-2-(Diphenylmethyl)pyrrolidine

175

5 .3 . Tertiary Amines

17 55 .3 .1 . Quinine/Cinchonidine/Quinidine

17 55 .3 .2 . 2, 8-Dimethyl-6H,12H-5,11-methanodibenzo[b,f] [ 1,5 ]

diazocine (Troger's Base)

18 0

5 .3 .3 . Brucine

18 0

5 .3 .4 . Strychnine

18 15 .3 .5 . (R)- and (S)-Tetrahydroisoquinoline

18 15 .4 . Diamine Reagents

18 2

5 .4 .1 . 1,2-Diphenyl-1,2-diaminoethane

18 2

5 .4 .2 . N,N'-Substituted 1,2-diphenyl-1,2-diaminoethane

18 3

5 .5 . Databases Using Amine Chiral Solvating Agents

18 4

5 .5 .1 . N,a.-Dimethylbenzylamine (DMBA) 18 45 .5 .2 . Bis-1,3-methylbenzylamine-2-methylpropane (BMBA-pMe) 18 75 .5 .3 . (R-a-Methoxy-a-trifluoromethylphenylacetic Aci d

(MTPA)/BMBA-pMe

18 9

6 . Miscellaneous Organic-based Chiral Derivatizing

and Solvating Agents

190

6.1 . Amides

19 16 .1 .1 . N-(3,5-Dinitrobenzoyl)-1-phenylethylamine (DNB-PEA)

19 16 .1 .2 . N-(3,5-Dinitrobenzoyl)-L-leucine (DNB-Leu)

19 36 .1 .3 . N-(3,5-Dinitrobenzoyl)phenylglycine

19 56 .1 .4 . N-(3,5-Dinitrobenzoyl)-4-amino-3-methyl-1,2,3,4 -

tetrahydrophenanthrene (Whelk-O-1)

19 5

6 .1 .5 . N-1-(1-Naphthyl)ethyltrifluoroacetamide

19 66 .1 .6 . 1-(1-Naphthyl)ethyl Urea Derivative s

of Amino Acids (NEU-AA)

19 76 .1 .7 . Bis Allyl Amide Derivatives

19 8

6 .1 .7 .1 . N,N'-Diallyl-L-tartardiamidebis(4-tert-butylbenzoate)

19 86 .1 .7 .2 . (S,S)-trans-Acenaphthene-1,2-dicarboxyli c

acid bis allylamide

19 86 .1 .8 . (R)-Phenylglycinol-N-3,5-dinitrobenzoyl-O -

triethoxysilylpropylcarbamate

19 86 .1 .9 . N-Methyl Amide of (R)-N-Acetyl-4-methoxy Pheny l

Glycine

19 96 .1 .10 . N-(n-Butylamide) of (S)-2-Phenylcarbamoyloxypropioni c

Acid

19 96 .1 .11 . 2,2'-Oxybis [N-(1-phenylethyl)acetamide]

2006 .1 .12 . Tetrapeptide Species

20 06 .1 .13 . Tetraamidic Selector

2006 .2 . Lactams

20 16 .2 .1 . Dihydropyrimidone

20 26.2 .2 . Amino Acid Isocyanurate Derivatives

202

6 .3 . Aldehydes

20 36 .3 .1 . 15-Formyl-14-hydroxy-2,8-di thia[9](2,5 )pyridinophane

2036 .3 .2 . 2 ' -Methoxy- l ,1 '-binaphthalene-8-carbaldehyde

2036 .3 .3 . 2-Hydroxy-2 ' -nitrobenzoate-3-aldehyde-1,1' -

binaphthalene

20 46.3 .4. 2-Hydroxy-2'-substituted-3-aldehyde-1,1' -

binaphthalene

20 56 .4 . Ketones

20 56 .4 .1 . 1-Menthone

20 56 .4 .2 . (S)-(+)-2-Propylcyclohexanone

2066 .5 . Isocyanates

2066 .5 .1 . 1-Phenylethyl Isocyanate (PE-I)

2066 .5 .2 . 1-( 1 -Naphthyl)ethyl Isocyanate (NE-I)

20 86 .5 .3 . Phenylethy Isothiocyanate (PE-IS)/Naphthylethy l

Isothiocyanate (NE-IS)

20 96 .5 .4 . a-Methoxy-a-(trifluoromethyl)benzylIsocyanate

2106 .5 .5 . 2,3,4,6-Tetra-O-acetyl-ß-D-glucopyranosy l

Isothiocyanate

2106 .5 .6 . (S)-2-Chloro-2-fluoroethanoyl Isocyanate

21 16 .6 . Miscellaneous Reagents

21 16 .6 .1 . 2,2-Dimethoxypropane

21 16 .6.2 . (-)-Chloromethylmenthyl Ether

21 26 .6.3 . 2-Oxazolidones

21 36 .6 .4 . 5(R)-Methyl- l -(chloromethyl)-2-pyrrolidinone

21 46 .6 .5 . 5-Methyl-5-phenylpyrroline N-oxide

21 56.6 .6. (S)-2[(R)-Fluoro(phenyl)methyl]oxirane

21 56 .6 .7 . (S)-Triazine Selector

21 66.6 .8 . 2-Deuterio-2, 3-dihydro-2-methyl-6 -

nitrobenzothiophene-1-oxide

21 66.6 .9 . 3 a-Benzhydryl-3, 3 a,4,5-tetrahydro-2H -

cyclopenta[b]furan

21 76 .6 .10 . Camphor-l0-sulfonic Acid (CSA)

21 76 .6 .11 . Menthyl Chloroformate

2196 .6 .12 . (N-Methylphenylsulfoximidoyl)methyl Lithium

2206.6 .13 . Coumarin Dimer

22 16 .6 .14 . Di-O-benzoyl Tartrate/Di-O-p-toluoyl Tartrate

22 1

6 .6 .15 . Dibenzoyl-L-tartaric Acid Anhydride

22 26 .6 .16 . DNA

22 36 .6 .17 . 5,8-Bis(aminomethyl)-1,12-dimethylbenzo[c ]

phenanthrene

22 36 .6 .18 . 2'-Methoxy-1,1'-binaphthalene-2-

carbohydroxymoyl Chloride (MBCC)

2236 .7 . Self-discrimination of Chiral Compounds

22 46 .8 . High-throughput Optical Purity Measurements

227

7 . Reagents Incorporating Phosphorus, Selenium, Boron ,and Silicon Atoms

22 9

7 .1 . Phosphorus-containing Reagents

23 07 .1 .1 . Phosphorus(V) Reagents

23 07 .1 .1 .1 . Phosphinic Amides (Phosl)

2307 .1 .1 .2 . Phosphinothioic Acids (Phos2)

23 17 .1 .1 .3 . cis-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2 -

oxazophospholidin-2-one(Phos3)

2347 .1 .1 .4 . (2-Chloro-4(R),5(R)-dimethyl-2-oxo-1,3,2 -

dioxaphospholane(Phos4)

2367.1 .1 .5 . L-Menthylphenylchlorophosphine Oxide (Phos5)

23 67 .1 .1 .6 . 2-Chloro-5,5-dimethyl-4-phenyl-1,3,2-

dioxaphosphorinane-2-oxide(Phos6)

23 67 .1 .1 .7 . O,O-Di-(2-(S)-(N,N-diethyl-2-hydroxypropyl )

phosphonate (Phos7)

23 77 .1 .1 .8 . 2-Chloro-3-phenyl-1,3,2-diazaphosphabicyclo

[3 .3 .0]octane-2-oxide (Phos8)

23 87 .1 .1 .9 . Methyl Phosphonic Dichloride (Phos9)/

Methyl Phosphonothioic Dichloride (PhoslO)

23 97 .1 .1 .10. O,O-Diphenyldithioic Acid (Phosl 1)

23 97 .1 .1 .11 . 1,1'-Binaphthyl-2,2 ' -diylphosphoric Acid (Phos12) 240

7 .1 .2 . Phosphorus(III) Reagents

24 27 .1 .2 .1 . Diazaphospholidines(Phos13-Phos20)

2427 .1 .2 .2 . 1,3,2-Dioxaphospholanes(Phos21-Phos27)

2467 .1 .2 .3 . Dimenthyl Chlorophosphite (Phos28)

24 87 .1 .2 .4. Dichloromenthylphosphine (Phos29)

24 87 .1 .2 .5 . Phosphorus Trichloride (Phos30)

2497 .1 .2 .6 . Hexaalkylphosphorus Triamides (Phos31)

2497 .1 .2 .7 . a-l-Phenylethylamino Trisaminoamine (Phos32)

2497 .1 .2.8 . [5] HELOL Phosphite (Phos33)

2497 .1 .3 . Ionic Reagents-TRISPHAT, BINPHAT, and BINTROP

2507 .1 .4 . Configurational Analysis of Phosphates

2607 .1 .4 .1 . Oxygen Isotope Methods

2607 .1 .4 .2 . ROESY Studies

26 37 .1 .5 . Summary

2647 .2. Selenium-containing Reagents

2647 .2 .1 . 4-Methyl-5-phenyloxazolidine-2-se lone

2647 .2 .2 . (R,R)-N,N'-Dimethylcyclohexyl-1,2-diazaselenophospholine 26 67 .2 .3 . 2-Phenylselenopropionic Acid

2677 .2 .4. 1,2,3-Selenadiazoles

2677 .3 . Boron-containing Reagents

2687 .3 .1 . 2-(1-Methoxyethyl)phenylboronic Acid

2687 .3 .2 . Phenylboronic Acid

2697 .3 .3 . Boric Acid [B(OH) 3 ]

270

7 .3 .4 . Camphanylboronic Acid

27 07 .3 .5 . 4S,5R-4-Methyl-5-phenyl-1,3,2-oxazaborolidine

(Ephedrine Borane)

27 17 .3 .6 . (S)-(+)-N-Acetylphenylglycine Boronic Acid

27 17 .3 .7 . 1-Benzamido-l-(2-methylphenyl)methaneboronic Acid

27 17 .3 .8 . 2-Formylphenylboronic Acid

2727.3 .9. 2,2 ' -(1,2-Phenylene)bis[(4R,5R)-4,5-diphenyl -

1,3,2-dioxaborolane

2727 .3 .10. (1-Chloroalkyl)boronates

27 37 .4 . Silyl-containing Reagents

27 47 .4 .1 . Menthylphenylsilylacetic Acid

27 47 .4 .2 . (Benzylmethylphenylsilyl)methylamine

27 47 .4 .3 . Monochlorosilanes

27 5

8 . Host Compounds as Chiral NMR Discriminating Agents

27 8

8 .1 . Cyclodextrins

27 98 .1 .1 . Introduction

2798 .1 .2 . Native Cyclodextrins

2808 .1 .2 .1 . Lanthanide Coupling to Native Cyclodextrins

2868 .1 .3 . Neutral Cyclodextrin Derivatives

2878 .1 .3 .1 . Hexakis(2,3,6-tri-O-methyl)-a-cyclodextri n

(TM-a-CD)/Heptaki s(2,3,6-tri-O-methyl ) -(3-cyclodextrin (TM-0-CD) - (Permethyl CDs)

28 78 .1 .3 .2 . Heptakis(2,6-di-O-methyl)-(3-cyclodextri n

(2,6-DM-(3-CD)

28 98 .1 .3 .3 . Benzylated and Benzoylated Cyclodextrins

2908 .1 .3 .4 . Carbamoylated Cyclodextrins

2908 .1 .3 .5 . Octakis(3-O-butanoyl-2,6-di-O-pentyl)-

y-cyclodextrin (BP-CD)

29 18 .1 .3 .6 . Hydroxyethyl and Hydroxypropy l

Cyclodextrins (HE-CD, HP-CD)

29 1

8 .1 .3 .7 . Heptakis(2,3-di-O-acetyl)-ß-CD (2,3-DA-0-CD)

29 18 .1 .3 .8 . Mono(2-acetylamino-2-deoxy)-, Mono

(3-acetylamino-3-deoxy)- and Mono(6-acetylamino-6-deoxy)- ß-cyclodextri n

(AA-13-CD)

292

8 .1 .3 .9 . Mono-3,6-anhydro-ß-cyclodextrin

2928 .1 .3 .10. Heptakis(3-O-acetyl-2,6-di-O-pentyl) -

3-cyclodextrin

292

8 .1 .3 .11 . Octakis(2,6-di-O-pentyl-3-O-trifluoroacetyl)-y-cyclodextrin

292

8 .1 .3 .12 . Cyanoethylated-ß-cyclodextrin

292

8 .1 .3 .13 . Per-O-octyl-a-cyclodextrin

293

8 .1 .3 .14 . Biphenyl-capped-f3-cyclodextrin

293

8 .1 .3 .15 . Heptakis(2,3,6-tri-O-acetyl)-ß-CD (TA-0-CD)

293

8 .1 .4 . Anionic Cyclodextrin Derivatives

293

8 .1 .4 .1 . Carboxymethylated Cyclodextrins (CM-CD)

293

8 .1 .4 .2 . Heptakis(6-carboxymethylthio-6-deoxy) -ß-cyclodextrin (6-CMT-ß-CD)

2968 .1 .4 .3 . Sulfobutylether-ß-cyclodextrin (SBE-ß-CD)

2968 .1 .4 .4 . Heptakis(2,3-di-O-acetyl-6-sulfo)-ß-CD

(HDAS-ß-CD)

297

8 .1 .4 .5 . Sulfated Cyclodextrins (S-CD)

29 8

8 .1 .5 . Cationic Cyclodextrin Derivatives

29 8

8 .1 .5 .1 . Amino-substituted Cyclodextrins

29 8

8 .1 .5 .2 . Bis(6-trimethylammonio)-ß-cyclodextri n(TMA- (3-CD)

2998 .1 .5 .3 . Mono(6-xylylenediamine)-ß-cyclodextrin (X-ß-CD) 29 9

8 .1 .6 . Summary

29 9

8 .2 . Crown Ethers

30 0

8 .2 .1 . Introduction

300

8 .2 .2 . (18-Crown-6)-2,3,11,12-tetracarboxylic Acid(18-C-6-TCA)

30 18 .2 .2 .1 . Amide Derivatives of (18-Crown-6)-2,3,11,12-

tetracarboxylic Acid

30 3

8 .2 .3 . (18-Crown-6)-2,3,11,12-derivatives

30 3

8 .2 .4. Crown Ethers Incorporating a 2,2'-Dihydroxy-1,1' -binaphthalene Unit

30 58 .2 .5 . Glycoside-derived Crown Ethers

3058 .2 .6. Crown Ether-like Compounds with

Nitrogen-heterocyclic Units

306

8 .2 .7 . Triazole-18-crown-6 Ether

308

8 .2 .8 . Crown Ether-like Compounds with Phenol Units

3088 .2 .9 . Aza Crown Ethers

3098 .3 . Calixarenes and Calixresorcarenes

31 18 .3 .1 . Introduction

31 1

8 .3 .2 . Calix[4]resorcarenes

312

8 .3 .3 . Calixarenes

3158 .3 .4 . Summary

3198 .4 . Receptor Compounds for Carboxylic Acids

3208 .5 . Cyclic Peptides

3238 .6 . Miscellaneous Receptor Compounds

3248 .6 .1 . Cyclic Tetraamidic Reagent

3248 .6 .2 . Cyclosophoraoses (Cyclic(1-2)-ß-D-glucans)

3258 .6 .3 . Glycophane Receptor

3258 .6.4 . Cyclophane Receptors

32 68 .6 .5 . Cryptophane Receptor

3268 .6.6 . Receptor for Secondary Amines

3278 .6.7 . Spirobisindane Receptor

32 78 .6.8 . Receptors for Diols

32 88 .6.9 . 1,1 ' -Binaphthalene-based Receptors

328

8 .7 . Enzymes

32 98 .7 .1 . Calmodulin

3298 .7 .2 . Chymotrypsin

330

9. Chiral Discrimination with Metal-based Reagents

33 1

9 .1 . Introduction

33 19 .2 . Lanthanide Complexes

33 29 .2 .1 . Introduction

33 29 .2 .2 . Peak Broadening with Lanthanide Shift Reagents

3359 .2 .3 . Catalytic Properties of Lanthanide Ions

33 79 .2 .4. Application of Lanthanide tris ß-diketonates

33 89 .2 .1 .1 . Discrimination of Prochiral Nuclei

33 99 .2 .1 .2 . Analysis of Deuterium-Substituted

Compounds

34 19 .2 .1 .3 . Analysis of Compounds Chiral by Virtu e

of Slow Rotation

34 29 .2 .4 .1 . Analysis of Compounds Chiral by Virtu e

of Geometrical Constraints

3449 .2 .5 . Miscellaneous Applications of Lanthanide

tris 13-diketonates

3469 .2 .6 . Analysis of Chiral Metal Complexes

3489 .2 .7 . Assignment of Absolute Stereochemistry

35 19 .2 .8 . Pr(III) Complex of Tetraphenylimidodiphosphinate-

Pr(tpip)3

3549 .2 .9 . Binuclear Lanthanide-silver Reagents

35 59 .2 .9 .1 . Analysis of Organic Salts

35 89 .2 .10 . Aqueous Lanthanide Shift Reagents

35 99 .2 .10 .1 . Complexes of Propylenediaminetetraacetate

(pdta)

360

9.2 .10 .2 . Complexes of N,N,N',N'-Tetrakis(pyridylmethyl )propylene Diamine (TPPN)

36 19 .2 .10.3 . Complexes with Other Ligands

362

9.2 .10 .4 . Complexes with Tetraazocyclodecan eMacrocyclic Ligands

3649 .3 . Transition Metal Complexes

365

9 .3 .1 . Palladium Complexes

365

9 .3 .1 .1 . Bridged Dimers with Amine Ligands

365

9 .3 .1 .2 . Miscellaneous Palladium Complexes

37 2

9 .3 .2 . Platinum Complexes

37 4

9 .3 .2 .1 . Complexes with Diphosphine Ligands

37 4

9 .3 .2 .2 . Complexes with Amine Ligands

37 5

9 .3 .2 .3 . Analysis of Geometrical Isomers

37 8

9 .3 .3 . Rhodium Complexes

37 8

9 .3 .3 .1 . Rhodium Dimer-[Rh2(MTPA)4]

37 8

9 .3 .3 .2. Miscellaneous Rhodium Complexes

384

9 .3 .4 . Cobalt Complexes

38 59 .3 .4 .1 . Complexes with Porphyrin Ligands

38 5

9 .3 .4.2 . Analysis of Geometrical Isomers

38 7

9 .3 .4 .3 . Analysis of DNA

38 9

9 .3 .5 . Zinc Complexes

389

9 .3 .6 . Ruthenium Complexes

3929 .3 .7 . Nickel Complexes

394

9 .3 .8 . Copper Complexes

394

9 .3 .9 . Silver Complexes

395

9 .3 .10 . Tin Complexes

396

9 .3 .11 . Titanium Complexes

39 7

9 .3 .12 . Tungsten Complexes

39 7

9 .3 .13 . Molybdenum Complexes

39 7

9 .3 .14 . Mercury Complexes

39 7

9 .3 .15 . Osmium Complexes

39 8

9 .3 .16 . Uranium Complexes

39 8

10. Chiral NMR Discrimination with Highl yOrdered Systems

399

10 .1 . Introduction

399

10 .2 . Liquid Crystals

40010.2 .1 . Introduction

400

10 .2 .2 . Early Studies with Liquid Crystals

40 1

10 .2 .3 . 2 H NMR Analysis of Labeled Compounds

40 3

10 .2 .4 . Natural Abundance 2H NMR Analysis

41 0

10 .2 .5 . 13 C NMR Analysis

41 2

10 .2 .6 . ' H NMR Analysis

41 410 .2 .7 . 19F NMR Analysis

41 4

10 .2 .8 . Analysis Using Other Nuclei

41 5

10 .2 .9 . Miscellaneous Studies with LiquidCrystals

41 510 .3 . Micelles and Gels

41 610 .4. Ionic Liquids

41 910 .5 . Polymers

420

10 .5 .1 . Cellulose-carbamate Polymers

420

10 .5 .2 . Poly 3- and 4-((S-(a-Methylbenzylcarbamoyl )phenyl Isocyanate

42 110 .5 .3 . Poly(ester/ -sulfoxides)

42 110.5 .4. Chirasil-val

42 210.5 .5 . Poly(N-1-anthrylmaleimide)

42 210 .5 .6. Poly [(1-6)-2,5-anhydro-3,4-di-O-methyl -

n-glucitol]

423

10 .6 . Aggregation of Achiral Compounds into Chiral Assemblies

42310 .7 . Solid-state NMR Spectroscopy

42510 .7 .1 . Tri-O-thymotide Clathrates

42510 .7 .2 . Cholic Acid Channels

42610 .7 .3 . Analysis of Polymer-bound Compounds

42 7

References

428

Index

537