Preface ....................................................... xxi
Acknowledgments ............................................. xxiii
1. Introduction ................................................. 1
1.1. Chiral Derivatizing Agents .............................. 1
1.2. Chiral Solvating Agents ................................. 2
1.3. Overview of Chiral Reagents and Methodologies ........... 4
1.4. Future Prospects ........................................ 6
2. Aryl-Containing Carboxylic Acids ............................. 8
2.1. Introduction ............................................ 8
2.2. α-Methoxy-α-trifluoromethylphenylacetic Acid (MTPA-
Mosher's Reagent) ...................................... 11
2.2.1. Analysis of Secondary Alcohols .................. 13
2.2.2. Analysis of Secondary Diols and Polyols ......... 19
2.2.3. Analysis of Primary Alcohols .................... 25
2.2.4. Analysis of Tertiary Alcohols ................... 26
2.2.5. Analysis of Secondary Amines .................... 26
2.2.6. Analysis of Primary Amines ...................... 28
2.2.7. Use as a Chiral Solvating Agent ................. 29
2.2.8. Use of MTPA Derivatives with Paramagnetic
Lanthanide Chelates ............................. 30
2.2.9. Use of MTPA Derivatives with Diamagnetic
Lanthanide Chelates ............................. 34
2.2.10.Preparation of MTPA Derivatives ................. 35
2.2.11.Liquid Chromatography-NMR Spectroscopy
of MTPA Derivatives ............................. 35
2.2.12.Database Methods with MTPA ...................... 35
2.3. α-Methoxyphenylacetic Acid (O-methyl Mandelic
Acid-MPA) .............................................. 38
2.3.1. Analysis of Secondary Alcohols .................. 39
2.3.2. Analysis of Diols ............................... 42
2.3.3. Analysis of Primary Alcohols .................... 43
2.3.4. Analysis of Amines .............................. 44
2.3.5. Analysis of Sulfoxides .......................... 45
2.3.6. Variable-temperature Method for Assigning
Absolute Stereochemistry ........................ 46
2.2.7. Barium(II) Method for Assigning Absolute
Stereochemistry ................................. 47
2.3.8. Use of MPA Derivatives with Lanthanide
Chelates ........................................ 48
2.3.9. Use as a Chiral Solvating Agent ................. 49
2.3.10.Preparation of MPA Derivatives-The "Mix and
Shake" Method ................................... 50
2.4. Mandelic Acid (2-Hydroxy-2-phenyl Acetic Acid) (MA) .... 51
2.5. O-Acetyl Mandelic Acid (2-Acetoxy-2-phenyl Acetic
Acid) (O-AMA) .......................................... 53
2.6. Tetrahydropyranyl-protected Mandelic Acid [(2R)-2-
phenyl-2-[(2S)-tetrahydro-2-pyranyloxy] Ethanoic
Acid] .................................................. 56
2.7. O-Nitromandelic Acid ................................... 56
2.8. 2-Phenylpropionic Acid (2-PPA) ......................... 57
2.9. 2-Methoxy-2-phenylpropionic Acid ....................... 58
2.10.3-Phenylbutanoic Acid (3-PBA)/2-Phenylbutanoic
Acid (2-PBA) ........................................... 58
2.11.α-Methyl-α-methoxy(pentafluorophenyl) (Acetic Acid) .... 60
2.12.α-Cyano-α-fluorophenylacetic Acid (CFPA)/α-Cyano-α-
fiuoronaphfhylacetic Acid (CFNA)/a-Cyano-α-fluoro-
/p-tolylacetic Acid (CFTA) ............................. 60
2.13.N-Boc Phenylglycine (BPG) .............................. 62
2.14.l,5-Difluoro-2,4-dinitrobenzene and Derivatives ........ 63
2.14.1.N-(5-Fluoro-2,4-dinitrophenyl)-l-
phenylefhylarnide ............................... 64
2.14.2.l-Fluoro-2,4-dinitrophenyl-5-(5)-alanine
Amide (Marfey's Reagent) ........................ 65
2.15.2-Fluoro-2-phenylacetic Acid/2-Fluoro-2-
(l-naphthyl)propionic Acid/2-Fluoro-2-(2-naphthyl)
propionic Acid ......................................... 66
2.16.a-Methoxy-a-(l-naphfhyl) Acetic Acid
(1 -NMA)/oc-Methoxy-a-(2-naphthyl) Acetic Acid
(2-NMA) ................................................ 67
2.17.2-(l-Naphthyl)-2-phenylacetic Acid ..................... 70
2.18.2-Methoxy-2-( 1 -naphthyl) Propionic Acid (MocNP) ...... 71
2.19.1 -Methoxy-2,3-dihydro-1 H-cyclopenta
[alnaphthalene-1-carboxylic Acid ..................... 72
2.20.O-Aryl Lactic Acids .................................... 72
2.21.α-(2-Anthryl)-α-methoxyacetic Acid (2-AMA)/oc-
(9-Anthryl)-α-methoxyacetic Acid (9-AMA) ............... 74
2.22.(α-[l-(9-Anthryl)]-2,2,2-trifluoroethoxy)acetic Acid ... 78
2.23.2-Methoxy-2-(9-phenanthryl)propionic Acid .............. 78
2.24.Summary ................................................ 79
2.24.1.Analysis of Primary Alcohols .................... 79
2.24.2.Analysis of Secondary Alcohols .................. 79
2.24.3.Analysis of Tertiary Alcohols ................... 80
2.24.4.Analysis of Primary Amines ...................... 80
2.24.5.Analysis of Secondary Amines .................... 81
3. Other Carboxylic Acid-based Reagents ........................ 82
3.1. Camphanic Acid ......................................... 82
3.2. Menthoxyacetic Acid (MAA) .............................. 86
3.3. 2-(2,3-Anthracenedicarboximido)cyclohexane
Carboxylic Acid ........................................ 87
3.4. 3P-Acetoxy-A5-etiocholenic Acid ........................ 88
3.5. Naproxen ............................................... 89
3.6. 2-tert-ButyI-2-methyl-l,3-benzodioxoIe-4-carboxylic
Acid ................................................... 90
3.7. endo-3-BENZAMIDONORBORNANE-2-CARBOXYLIC ACID ........... 90
3.8. Coumarin-based Reagents ................................ 91
3.9. 2,2-Diphenylcyclopropane Carboxylic Acid ............... 91
3.10.Amide Derivatives of Kemp's Triacid .................... 91
3.11.Amino Acids ............................................ 92
3.11.1.N-Boc-phenylalanine ............................. 92
3.11.2.Isotopically Substituted Amino Acids ............ 92
3.12.(R)-(-)-(2,3,5,7-Tetranitro-9-fiuorenyloximino)
propanoic Acid ......................................... 93
3.13.2-Chloropropanoic Acid (2-C1-PA) .................. 93
3.14.Chlorofluoroacetic Acid ................................ 94
3.15.Perfluoropropoxy Propionic Acid/Perfluoro
Isopropropoxy Propionic Acid ........................... 94
3.16.2-Methylbutyric Acid ................................... 94
3.17.Lactic Acid and Derivatives ............................ 95
3.17.1.Trifluorolactic Acid ............................ 95
3.17.2.(S)-O-Acetyllactylchloride ...................... 95
3.18.Lasalocid .............................................. 96
3.19.Axial Chiral Carboxylic Acids .......................... 96
3.19.1.(+)-1 -[2-Carboxy-6-(trifluoromethyl)phenyl]
pyrrole-2-carboxylic Acid ....................... 96
3.19.2. 2'-Methoxy-l,l'-binaphthyl-2-carboxylic Acid
(MBNC) ......................................... 97
3.19.3. 2'-Methoxy-1,1 '-binaphthalene-8-carboxylic
Acid ........................................... 98
3.19.4. 2'-Octylcarbamoyl-l,l'-binaphthyl-2-
dicarboxylic Acid ............................. 100
3.19.5. 2-(2'-Methoxy-l'-naphthyl)-3,5-
dichlorobenzoic Acid(MNCB) .................... 100
4. Hydroxyl- and Thiol-Containing Reagents .................... 102
4.1. 2,2,2-Trifluorophenylethanol(TFPE) .................... 103
4.2. 2,2,2-Trifluoro-1 -(9-anthryl)ethanol (Pirkle's
Alcohol (TFAE) ........................................ 109
4.2.1. Analysis of Sulfoxides ......................... 109
4.2.2. Analysis of Lactones ........................... 110
4.2.3. Analysis of Lactams ............................ 111
4.2.4. Analysis of Oxaziridines ....................... 112
4.2.5. Analysis of Axial Chiral Compounds ............. 112
4.2.6. Analysis of Compounds that are Chiral by
Virtue of Slow Rotation ........................ 113
4.2.7. Analysis of Metal Complexes .................... 115
4.2.8. Analysis of Cyclophosphazenes .................. 116
4.2.9. Analysis of Phosphine Oxides ................... 117
4.2.10.Analysis of Calixarenes ........................ 118
4.2.11.Analysis of Other Substrates ................... 119
4.2.12.Use of Lanthanide Chelates with TFPE and
TFAE ........................................... 122
4.2.13.Use as a Chiral Derivatizing Agent ............. 123
4.3. Other Anthryl-based Reagents .......................... 123
4.3.1. Analogs of TFAE ................................ 123
4.3.2. Ethyl-2-(9-anthryl)-2-hydroxyacetate ........... 126
4.3.3. 2-(2,3-Anthracenedicarboximido)-l-
cyclohexanol ................................... 127
4.4. 2,2,2-Trifluoro-l-(l-pyrenyl)ethanol .................. 127
4.5. 2-(Trifluoromethyl)benzhydrol ......................... 127
4.6. 1-Phenylethanol ....................................... 128
4.7. Methyl Mandelate (MM) ................................. 129
4.8. Octahydro-8,9,9-trimethyl-5,8-methano-2tf-1 -
benzopuran-2-ol (Noe's Reagent) ....................... 130
4.9. Menthol ............................................... 132
4.10.Borneol ............................................... 135
4.11.(-)-10-Mercaptoisoborneol ............................. 135
4.12.(R)-(-)-Pantolactone .................................. 136
4.13.trans-Bis(hydroxydiphenylmethyl)-2,2-dimethyl-1,3-
dioxacyclopentane ..................................... 136
4.14.2-Hydroxy methy l-4,6-dimethyl-2-phenyl-l,3-dioxane ... 137
4.15.2-Butanol ............................................. 137
4.16.Assignment of Absolute Configuration Using
Glycosidation Shifts .................................. 138
4.16.1.Analysis of Di-and Polysaccharides ............ 141
4.16.2.P-D-and P-L-Fucofuranoside/
Arabinofuranoside ............................. 142
4.17.Linear Dextrins ....................................... 144
4.18.Axial Chiral (Atropoisomeric) Alcohols ................ 144
4.18.1.2,2'-Dihydroxy-l,l'-binaphthalene(BINOL) ....... 145
4.18.2.8,8'-Dihydroxy-l,l'-binaphthalene .............. 147
4.18.3.Alkyl-Substituted Binaphthols .................. 147
4.18.4.2'-Hydroxy-l,l'-binaphthyl-2-yl[(3,5-
dinitrobenzoyl) aminoJ(phenyl)acetate .......... 148
4.18.5.1,6-Di(o-chlorophenyl)-1,6-diphenylhexa-
2,4-diyne-l,6-diol ............................. 148
4.18.6.4,4'6,6'-Tetrachloro-2,2'-bis
(hydroxydiphenyImethyI) biphenyl ............... 148
4.19. Dio) and Dithiol Reagents ............................ 149
4.19.1.Butane-2,3-diol/Butane-2,3-thiol ............... 149
4.19.2.2,2-Dimethyl-l,3-propanediol ................... 150
4.19.3.l,l,2-Triphenyl-l,2-ethanediol ................. 151
4.19.4.Ethylene Dithiol ............................... 151
4.19.5.ααα'α'-Tetraphenyl-1,3-dioxolane-4,5-
dimethanols) (TADDOL) .......................... 151
5. Amine-based Reagents ....................................... 153
5.1. Primary Amines ........................................ 154
5.1.1. 1-Phenylethylamine (PEA)/1-(1-Naphthyl)
ethylamine (NEA)/l-(9-Anthryl)ethylamine
(AEA) .......................................... 154
5.1.2. Fluorinated Aryl Amines ........................ 161
5.1.3. 9-(l-Amino-2,2-dimethylpropyl)-9,10-
dihydroanthracene .............................. 161
5.1.4. (lS,2S)-l-Phenyl-2-amino-3-rnethoxy-l-
propanol ....................................... 162
5.1.5. Phenylglycinol ................................. 163
5.1.6. l-(3-Aminopropyl)-(5R,8S,10R)terguride ......... 163
5.1.7. 5-Amino-4-aryl-2,2-dimethyl-l,3-dioxans ........ 164
5.1.8. Amino Acids .................................... 164
5.1.8.1. Peptides .............................. 164
5.1.8.2. Phenylglycine methyl ester (PGME)/
Phenylglycine dimethyl-amide .......... 165
5.1.8.3. L-Cysteine ............................ 168
5.1.8.4. L-Proline ............................. 169
5.1.9. (1R,2R)-1 -(1',8'-Naphthalimide)-2-
aminocyclohexane Derivatives ................... 169
5.1.10.l-(l-Naphthyl)-2,2-dimethylpropylamine ......... 170
5.1.11.l-Methoxy-2-aminopropane ....................... 170
5.1.12.(+)-2-Amino-l-methoxymenth-8-ene ............... 171
5.2. Secondary Amines ...................................... 171
5.2.1. Ephedrine ...................................... 171
5.2.2. 2-Methyl Piperidine ............................ 173
5.2.3. (N-Methyl)-α-isosparteinium cation ............. 174
5.2.4. N-Boc-l-(l-naphthyl)ethylamine ................. 174
5.2.5. N-Methyl-D-(-)-glucamine ....................... 175
5.2.6. (S)-2-(Diphenylmethyl)pyrrolidine .............. 175
5.3. Tertiary Amines ....................................... 175
5.3.1. Quinine/Cinchonidine/Quinidine ................. 175
5.3.2. 2,8-Dimethyl-6H,12H-5,ll-methanodibenzo
[b,f](1,5) diazocine (Troger's Base) ............ 180
5.3.3. Brucine ........................................ 180
5.3.4. Strychnine ..................................... 181
5.3.5. (R)- and (S)-Tetrahydroisoquinoline ............ 181
5.4. Diamine Reagents ...................................... 182
5.4.1. l,2-Diphenyl-l,2-diaminoethane ................. 182
5.4.2. N,N'-Substituted l,2-diphenyl-l,2-
diaminoethane .................................. 183
5.5. Databases Using Amine Chiral Solvating Agents ......... 184
5.5.1. N,a-Dimethylbenzylamine (DMBA) ................. 184
5.5.2. Bis-l,3-methylbenzylamine-2-methylpropane
(BMBA-pMe) ..................................... 187
5.5.3. (R-α-Methoxy-α-trifluoromethylphenylacetic
Acid (MTPA)/BMBA-pMe ........................... 189
6. Miscellaneous Organic-based Chiral Derivatizing
and Solvating Agents ....................................... 190
6.1. Amides ................................................ 191
6.1.1. N-(3,5-Dinitrobenzoyl)-1 -phenylethylamine
(DNB-PEA) ....................................... 191
6.1.2. N-(3,5-Dinitrobenzoyl)-L-leucine(DNB-Leu) ...... 193
6.1.3. N-(3,5-Dinitrobenzoyl)phenylglycine ............ 195
6.1.4. N-(3,5'Dinitrobenzoyl)-4-amino-3-methyl-
1,2,3,4-tetrahydrophenanthrene (Whelk-O-1) ..... 195
6.1.5. N-1-(I-Naphthyl)ethyltrifluoroacetamide ........ 196
6.1.6. 1-(1-Naphthyl)ethyl Urea Derivatives
of Amino Acids (NEU-AA) ........................ 197
6.1.7. Bis Allyl Amide Derivatives 198
6.1.7.1. N,N'-Diallyl-L-tartardiamide bis(4-
tert-butylbenzoate) ................... 198
6.1.7.2. (S,S)-trans-Acenaphlhene-1,2-
dicarboxylic acid bis allylamide ...... 198
6.1.8. (R)-Phenylglycinol-N-3,5-dinitrobenzoyl-0-
triethoxysilylpropylcarbamate .................. 198
6.1.9. TV-Methyl Amide of (R)-N-Acetyl-4-mefhoxy
Phenyl Glycine ................................. 199
6.1.10.N-(n-Butylamide) of (5)-2-
Phenylcarbamoyloxypropionic Acid ............... 199
6.1.11.2,2'-Oxybisl/V-(1-phenylethyDacetamideJ ........ 200
6.1.12.Tetrapeptide Species ........................... 200
6.1.13.Tetraamidic Selector ........................... 200
6.2. Lactams ............................................... 201
6.2.1. Dihydropyrimidone .............................. 202
6.2.2. Amino Acid Isocyanurate Derivatives ............ 202
6.3. Aldehydes ............................................. 203
6.3.1. 15-Formyl-14-hydroxy-2,8-dithia[9](2,5)
pyridinophane .................................. 203
6.3.2. 2'-Methoxy-l,l'-binaphthalene-8-carbaldehyde ... 203
6.3.3. 2-Hydroxy-2'-nitrobenzoate-3-aldehyde-l,l'-
binaphthalene .................................. 204
6.3.4. 2-Hydroxy-2'-substituted-3-aldehyde-1,1'-
binaphthalene .................................. 205
6.4. Ketones ............................................... 205
6.4.1. 1-Menthone ..................................... 205
6.4.2. (S)-(+)-2-Propylcyclohexanone .................. 206
6.5. Isocyanates ........................................... 206
6.5.1. 1-Phenylethyl Isocyanate (PE-I) ................ 206
6.5.2. 1-(1-Naphthyl)ethyl Isocyanate (NE-I) .......... 208
6.5.3. Phenylethy Isothiocyanate (PE-IS)/
Naphthylethyl Isothiocyanate (NE-IS) ........... 209
6.5.4. α-Methoxy-a-(trifluoromethyl)benzyl
Isocyanate ..................................... 210
6.5.5. 2,3,4,6-Tetra-0-acetyl-(3-D-glucopyranosyl
Isothiocyanate ................................. 210
6.5.6. (5')-2-Chloro-2-fluoroethanoyl Isocyanate ...... 211
6.6. Miscellaneous Reagents ................................ 211
6.6.1. 2,2-Dimethoxypropane ........................... 211
6.6.2. (-)-Chloromethylmenthyl Ether .................. 212
6.6.3. 2-Oxazolidones ................................. 213
6.6.4. 5(R)-Methyl-l-(chloromethyl)-2-pyrrolidinone ... 214
6.6.5. 5-Methyl-5-phenylpyrroline N-oxide ............. 215
6.6.6. (5')-2|(R)-Fluoro(phenyl)methylloxirane ........ 215
6.6.7. (SyTriazine Selector ........................... 216
6.6.8. 2-Deuterio-2,3-dihydro-2-methyl-6-
nitrobenzothiophene-1-oxide .................... 216
6.6.9. 3α-Benzhydryl-3,3α,4,5-tetrahydro-2H-
cyclopenta[b]furan ............................. 217
6.6.10.Camphor-10-sulfonic Acid (CSA) ................. 217
6.6.11.Menthyl Chloroformate .......................... 219
6.6.12.(jV-Methylphenylsulfoximidoyl)methyl Lithium ... 220
6.6.13.Coumarin Dimer ................................. 221
6.6.14.Di-O-benzoyl Tartrate/Di-O-yp-toluoyl
Tartrate ....................................... 221
6.6.15.Dibenzoyl-L-tartaric Acid Anhydride ............ 222
6.6.16.DNA ............................................ 223
6.6.17.5,8-Bis(aminomethyl)-1,12-dimethylbenzo[c]
phenanthrene ................................... 223
6.6.18.2'-Methoxy-1,1 '-binaphthalene-2-
carbohydroxymoyl Chloride (MBCC) ............... 223
6.7. Self-discrimination of Chiral Compounds ............... 224
6.8. High-throughput Optical Purity Measurements ........... 227
7. Reagents Incorporating Phosphorus, Selenium, Boron,
and Silicon Atoms .......................................... 229
7.1. Phosphorus-containing Reagents ........................ 230
7.1.1. Phosphorus (V) Reagents ........................ 230
7.1.1.1. Phosphinic Amides (Phosl) ............. 230
7.1.1.2. Phosphinothioic Acids (Phos2) ......... 231
7.1.1.3. cis-2-Chloro-3,4-dimethyl-5-pheny1-
1,3,2-oxazophospholidin-2-one
(Phos3) ............................... 234
7.1.1.4. (2-Chloro-4(R),5(fi)-dimethyl-2-
oxo-l,3,2-dioxaphospholane (Phos4) .... 236
7.1.1.5. L-Menthylphenylchlorophosphine Oxide
(Phos5) ............................... 236
7.1.1.6. 2-Chloro-5,5-dimethyl-4-phenyl-
1,3,2-dioxaphosphorinane-2-oxide
(Phos6) ............................... 236
7.1.1.7. O,O-Di-(2-(S)-(N,N-diethyl-2-
hydroxypropyl) phosphonate (Phos7) .... 237
7.1.1.8. 2-Chloro-3-phenyl-1,3,2-
diazaphosphabicyclo [3.3.0]octane-2-
oxide (Phos8) ......................... 238
7.1.1.9. Methyl Phosphonic Dichloride
(Phos9)/Methyl Phosphonothioic
Dichloride (Phos10) ................... 239
7.1.1.10.O,O-Diphenyldithioic Acid (Phosl1) .... 239
7.1.1.11.l,l'-Binaphthyl-2,2'-diylphosphoric
Acid (Phosl2) ......................... 240
7.1.2. Phosphorus(III) Reagents ....................... 242
7.1.2.1. Diazaphospholidines (Phosl3-Phos20) ... 242
7.1.2.2. l,3,2-Dioxaphospholanes(Phos21-
Phos27) ............................... 246
7.1.2.3. Dimenthyl Chlorophosphite (Phos28) .... 248
7.1.2.4. Dichloromenthylphosphene (Phos29) ..... 248
7.1.2.5. Phosphorus Trichloride (Phos30) ....... 249
7.1.2.6. Hexaalkylphosphorus Triamides
(Phos31) .............................. 249
7.1.2.7. α-1-Phenylethylamino Trisaminoamine
(Phos32) .............................. 249
7.1.2.8. [5] HELOL Phosphite (Phos33) .......... 249
7.1.3. Ionic Reagents—TRISPHAT, BINPHAT, and
BINTROP ........................................ 250
7.1.4. Configurational Analysis of Phosphates ......... 260
7.1.4.1. Oxygen Isotope Methods ................ 260
7.1.4.2. ROESY Studies ......................... 263
7.1.5. Summary ........................................ 264
7.2. Selenium-containing Reagents .......................... 264
7.2.1. 4-Methyl-5-phenyloxazolidine-2-selone .......... 264
7.2.2. (R,R)-N,N'-Dimethylcyclohexyl-1,2-
diazaselenophospholine ......................... 266
7.2.3. 2-Phenylselenopropionic Acid ................... 267
7.2.4. 1,2,3-Selenadiazoles ........................... 267
7.3. Boron-containing Reagents ............................. 268
7.3.1. 2-(l-Methoxyethyl)phenylboronic Acid ........... 268
7.3.2. Phenylboronic Acid ............................. 269
7.3.3. Boric Acid [B(OH)3] ............................ 270
7.3.4. Camphanylboronic Acid .......................... 270
7.3.5. 4S,5R-4-Methyl-5-phenyl-1,3,2-
oxazaborolidine (Ephedrine Borane) ............. 271
7.3.6. (S)-(+)-N-Acetylphenylglycine Boronic Acid ..... 271
7.3.7. l-Benzamido-l-(2-methylphenyl)methaneboronic
Acid ........................................... 271
7.3.8. 2-Formylphenylboronic Acid ..................... 272
7.3.9. 2,2'-( 1,2-Phenylene)bis[(4R,5R)-4,5-
diphenyl-1,3,2-dioxaborolane ................... 272
7.3.10.(l-Chloroalkyl)boronates ....................... 273
7.4. Silyl-containing Reagents ............................. 274
7.4.1. Menthylphenylsilylacetic Acid .................. 274
7.4.2. (Benzylmethylphenylsilyl)methylamine ........... 274
7.4.3. Monochlorosilanes .............................. 275
8. Host Compounds as Chiral NMR Discriminating Agents ......... 278
8.1. Cyclodextrins ......................................... 279
8.1.1. Introduction ................................... 279
8.1.2. Native Cyclodextrins ........................... 280
8.1.2.1. Lanthanide Coupling to Native
Cyclodextrins ......................... 286
8.1.3. Neutral Cyclodextrin Derivatives ............... 287
8.1.3.1. Hexakis(2,3,6-tri-O-methyl)-α-
cyclodextrin (TM-α-CD)/Heptakis
(2,3,6-tri-O-methyl)-(β-cyclodextrin
(TM-(β-CD) - (Permethyl CDs) .......... 287
8.1.3.2. Heptakis(2,6-di-O-methyl)-P-
cyclodextrin (2,6-DM-p-CD) ............ 289
8.1.3.3. Benzylated and Benzoylated
Cyclodextrins ......................... 290
8.1.3.4. Carbamoylated Cyclodextrins ........... 290
8.1.3.5. Octakis(3-0-butanoyl-2,6-di-0-
pentyl)-y-cyclodextrin (BP-CD) ........ 291
8.1.3.6. Hydroxyethyl and Hydroxypropyl
Cyclodextrins (HE-CD, HP-CD) .......... 291
8.1.3.7. Heptakis(2,3-di-0-acetyl)-P-CD(2,3-
DA-P-CD) .............................. 291
8.1.3.8. Mono(2-acetylamino-2-deoxy)-, Mono
(3-acetylamino-3-deoxy)- and Mono
(6-acetylamino-6-deoxy)-β-
cyclodextrin (AA-β-CD) ................ 292
8.1.3.9. Mono-3,6-anhydro-β-cyclodextrin ....... 292
8.1.3.10.Heptakis(3-0-acetyl-2,6-di-O-
pentyl)-β-cyclodextrin ................ 292
8.1.3.11.Octakis(2,6-di-0-pentyl-3-0-
trifluoroacetyl)-γ-cyclodextrin ....... 292
8.1.3.12.Cyanoethylated-β-cyclodextrin ......... 292
8.1.3.13.Per-O-octyl-α-cyclodextrin ............ 293
8.1.3.14.Biphenyl-capped-β-cyclodextrin ........ 293
8.1.3.15.Heptakis(2,3,6-tri-0-acetyl)-β-CD
(TA-β-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)-β-cyclodextrin (6-CMT-β-CD) .... 296
8.1.4.3. Sulfobutylether-P-cyclodextrin
(SBE-β-CD) ............................ 296
8.1.4.4. Heptakis(2,3-di-O-acetyl-6-sulfo)-
β-CD (HDAS-β-CD) ...................... 297
8.1.4.5. Sulfated Cyclodextrins (S-CD) ......... 298
8.1.5. Cationic Cyclodextrin Derivatives .............. 298
8.1.5.1. Amino-substituted Cyclodextrins ....... 298
8.1.5.2. Bis(6-trimethylammonio)-β-
cyclodextrin (TMA-β-CD) ............... 299
8.1.5.3. Mono(6-xylylenediamine)-β-
cyclodextrin(X-β-CD) .................. 299
8.1.6. Summary ........................................ 299
8.2. Crown Ethers .......................................... 300
8.2.1. Introduction ................................... 300
8.2.2. (18-Crown-6)-2,3,ll,12-tetracarboxylic Acid
(18-C-6-TCA) ................................... 301
8.2.2.1. Amide Derivatives of (18-Crown-6)-
2,3,11,12-tetracarboxylic Acid ........ 303
8.2.3. (18-Crown-6)-2,3,ll,12-derivatives ............. 303
8.2.4. Crown Ethers Incorporating a 2,2'-Dihydroxy-
1,1'-binaphthalene Unit ........................ 305
8.2.5. Glycoside-derived Crown Ethers ................. 305
8.2.6. 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 ... 308
8.2.9. Aza Crown Ethers ............................... 309
8.3. Calixarenes and Calixresorcarenes ..................... 311
8.3.1. Introduction ................................... 311
8.3.2. Calix[4]resorcarenes ........................... 312
8.3.3. Calixarenes .................................... 315
8.3.4. Summary ........................................ 319
8.4. Receptor Compounds for Carboxylic Acids ............... 320
8.5. Cyclic Peptides ....................................... 323
8.6. Miscellaneous Receptor Compounds ...................... 324
8.6.1. Cyclic Tetraamidic Reagent ..................... 324
8.6.2. Cyclosophoraoses (Cyclic(l-2)-β-D-glucans) ..... 325
8.6.3. Glycophane Receptor ............................ 325
8.6.4. Cyclophane Receptors ........................... 326
8.6.5. Cryptophane Receptor ........................... 326
8.6.6. Receptor for Secondary Amines .................. 327
8.6.7. Spirobisindane Receptor ........................ 327
8.6.8. Receptors for Diols ............................ 328
8.6.9. l,l'-Binaphthalene-based Receptors ............. 328
8.7. Enzymes ............................................... 329
8.7.1. Calmodulin ..................................... 329
8.7.2. Chymotrypsin ................................... 330
9. Chiral Discrimination with Metal-based Reagents ............ 331
9.1. Introduction .......................................... 331
9.2. Lanthanide Complexes .................................. 332
9.2.1. Introduction ................................... 332
9.2.2. Peak Broadening with Lanthanide Shift
Reagents ....................................... 335
9.2.3. Catalytic Properties of Lanthanide Ions ........ 337
9.2.4. Application of Lanthanide tris β-diketonates ... 338
9.2.1.1. Discrimination of Prochiral Nuclei .... 339
9.2.1.2. Analysis of Deuterium-Substituted
Compounds ............................. 341
9.2.1.3. Analysis of Compounds Chiral by
Virtue of Slow Rotation ............... 342
9.2.4.1. Analysis of Compounds Chiral by
Virtue of Geometrical Constraints ..... 344
9.2.5. Miscellaneous Applications of Lanthanide
tris β-diketonates ............................. 346
9.2.6. Analysis of Chiral Metal Complexes ............. 348
9.2.7. Assignment of Absolute Stereochemistry ......... 351
9.2.8. Pr(III) Complex of
Tetraphenylimidodiphosphinate-Pr(tpip)3 ........ 354
9.2.9. Binuclear Lanthanide-silver Reagents ........... 355
9.2.9.1. Analysis of Organic Salts ............. 358
9.2.10.Aqueous Lanthanide Shift Reagents .............. 359
9.2.10.1.Complexes of
Propylenediaminetetraacetate (pdta) ... 360
9.2.10.2.Complexes of N,N,N',N'-Tetrakis
(pyridylmethyl) propylene Diamine
(TPPN) ................................ 361
9.2.10.3.Complexes with Other Ligands .......... 362
9.2.10.4.Complexes with Tetraazocyclodecane
Macrocyclic Ligands ................... 364
9.3. 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 ..... 372
9.3.2. Platinum Complexes ............................. 374
9.3.2.1. Complexes with Diphosphine Ligands .... 374
9.3.2.2. Complexes with Amine Ligands .......... 375
9.3.2.3. Analysis of Geometrical Isomers ....... 378
9.3.3. Rhodium Complexes .............................. 378
9.3.3.1. Rhodium Dimer—[Rh2(MTPA)4] ............ 378
9.3.3.2. Miscellaneous Rhodium Complexes ....... 384
9.3.4. Cobalt Complexes ............................... 385
9.3.4.1. Complexes with Porphyrin Ligands ...... 385
9.3.4.2. Analysis of Geometrical Isomers ....... 387
9.3.4.3. Analysis of DNA ....................... 389
9.3.5. Zinc Complexes ................................. 389
9.3.6. Ruthenium Complexes ............................ 392
9.3.7. 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 ............................. 397
9.3.12.Tungsten Complexes ............................. 397
9.3.13.Molybdenum Complexes ........................... 397
9.3.14.Mercury Complexes .............................. 397
9.3.15.Osmium Complexes ............................... 398
9.3.16.Uranium Complexes .............................. 398
10.Chiral NMR Discrimination with Highly Ordered Systems ...... 399
10.1.Introduction .......................................... 399
10.2.Liquid Crystals ....................................... 400
10.2.1.Introduction ................................... 400
10.2.2.Early Studies with Liquid Crystals ............. 401
10.2.3.2HNMR Analysis of Labeled Compounds ............ 403
10.2.4.Natural Abundance 2HNMR Analysis ............... 410
10.2.5.I3CNMR Analysis ................................ 412
10.2.6.'HNMR Analysis ................................. 414
10.2.7.I9F NMR Analysis ............................... 414
10.2.8.Analysis Using Other Nuclei .................... 415
10.2.9.Miscellaneous Studies with Liquid Crystals ..... 415
10.3.Micelles and Gels ..................................... 416
10.4.Ionic Liquids ......................................... 419
10.5.Polymers .............................................. 420
10.5.1.Cellulose-carbamate Polymers ................... 420
10.5.2.Poly 3- and 4-((S-(α-Methylbenzylcarbamoyl)
phenyl Isocyanate .............................. 421
10.5.3.Poly(ester/β-sulfoxides) ....................... 421
10.5.4.Chirasil-val ................................... 422
10.5.5.Ро1у(N-1 -anthrylmaleimide) .................... 422
10.5.6.Poly [(l-6)-2,5-anhydro-3,4-di-O-methyl-
D-glucitol] .................................... 423
10.6.Aggregation of Achiral Compounds into Chiral
Assemblies ............................................ 423
10.7.Solid-state NMR Spectroscopy .......................... 425
10.7.1.Tri-O-thymotide Clathrates ..................... 425
10.7.2.Cholic Acid Channels ........................... 426
10.7.З.Analysis of Polymer-bound Compounds ............ 427
References .................................................... 428
Index ......................................................... 537
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