Preface xiii
Abbreviations xv
Volume 1
1. The Role of Protective Groups in Organic Synthesis 1
Properties of a Protective Group 1
Historical Development 1
Development of New Protective Groups 2
Selection of a Protective Group from This Book 3
Synthesis of Complex Substances. Two Examples (As Used in the Synthesis of Himastatin and Palytoxin) of the Selection Introduction and Removal of Protective Groups 4
Synthesis of Himastatin 4
Synthesis of Palytoxin Carboxylic Acid 8
2. Protection for the Hydroxyl Group Including 12- and 13- Diols 13
Ethers 22
Substituted Methyl Ethers 30
Substituted Ethyl Ethers 78
Methoxy- Substituted Benzyl Ethers 136
Silyl Ethers 191
Migration of Silyl Groups 193
Cleavage 226
Esters 254
Proximity Assisted Deprotection for Ester Cleavage 313
Miscellaneous Esters 320
Sulfonates Sulfenates and Sulfinates as Protective Groups for Alcohols 321
Carbonates 330
Carbamate Protection of Alcohols 356
Protection for 12- and 13- Diols 359
Monoprotection of Diols 360
Cyclic Acetals and Ketals 383
Chiral Ketones 443
Cyclic Ortho Esters 444
Silyl Derivatives 452
Cyclic Carbonates 461
Cyclic Boronates 464
3. Protection for Phenols and Catechols 469
Protection for Phenols and Catechols 472
Ethers 472
Silyl Ethers 518
Esters 524
Carbonates 530
Carbamates 533
Phosphinates 534
Sulfonates 535
Protection for Catechols (12- Dihydroxybenzenes) 540
Cyclic Acetals and Ketals 540
Cyclic Esters 545
Protection for 2- Hydroxybenzenethiols 546
4. Protection for the Carbonyl Group 549
Acetals and Ketals 553
Acyclic Acetals and Ketals 553
Cyclic Acetals and Ketals 568
Chiral Acetals and Ketals 600
Dithio Acetals and Ketals 604
Acyclic Dithio Acetals and Ketals 604
Cyclic Dithio Acetals and Ketals 609
Monothio Acetals and Ketals 628
Acyclic Monothio Acetals and Ketals 628
Cyclic Monothio Acetals and Ketals 631
Miscellaneous Derivatives 634
O- Substituted Cyanohydrins 634
Substituted Hydrazones 637
12- Adducts to Aldehydes and Ketones 650
Protection of the Carbonyl Group as an Enolate Anions Enol Ethers Enamines and Imines 657
Lithium Diisopropylamide (LDA) 657
Monoprotection of Dicarbonyl Compounds 659
Selective Protection of ¿- and ß- Diketones 659
Cyclic Ketals Monothio and Dithio Ketals 664
5. Protection for the Carboxyl Group 667
Esters 674
General Preparations of Esters 674
General Cleavage of Esters 679
Transesterification 683
Enzymatically Cleavable Esters 690
Substituted Methyl Esters 700
2- Substituted Ethyl Esters 719
Substituted Benzyl Esters 752
Silyl Esters 773
Activated Esters 777
Miscellaneous Derivatives 779
Stannyl Esters 791
Amides and Hydrazides 792
Amides 800
Protection of Sulfonic Acids 808
Protection of Boronic Acids 812
6. Protection for the Thiol Group 819
Thioethers 822
S- Diphenylmethyl Substituted S- Diphenylmethyl and S- Triphenylmethyl Thioethers 838
4- Methoxytrityl (Mtt-SR) Thioether 842
Substituted S- Methyl Derivatives: Monothio Dithio and Aminothio Acetals 846
Substituted S- Ethyl Derivatives 858
Silyl Thioethers 864
Thioesters 864
Thiocarbonate Derivatives 866
Thiocarbamate Derivatives 868
Miscellaneous Derivatives 869
Unsymmetrical Disulfides 869
Sulfenyl Derivatives 871
Protection for Dithiols: Dithio Acetals and Ketals 874
Protection for Sulfides 875
S-P Derivatives 876
Protection for the Amino Thiol Group 877
Protection for Selenols 877
Volume 2
7. Protection for the Amino Group 879
Introduction to Amines 891
Carbamates 891
Substituted Ethyl Carbamates 905
Carbamates Cleaved by a 16- Elimination 957
Cleavage by ß- Elimination 959
Photolytically Cleaved Carbamates 964
Miscellaneous Carbamates 970
Urea- Type Derivatives 972
Amides 973
Transamidation 974
Assisted Cleavage of Amides 991
Amide Cleavage Induced by Nitro Group Reduction 991
Amide Cleavage Induced by Release of an Alcohol 992
Amides Cleaved by Other Chemical Reactions 992
Bisprotection of Amines 993
Special -NH Protective Groups 1010
N- Alkyl and N- Aryl Amines 1010
Imine Derivatives 1042
Enamine Derivatives 1050
N- Heteroatom Derivatives 1053
N- Metal Derivatives 1054
N- N Derivatives 1057
N- P Derivatives 1063
N- Si Derivatives 1066
N- S Derivatives 1067
N- Sulfenyl Derivatives 1067
Protection of Amino Alcohols 1096
Protection for Imidazoles Pyrroles Indoles and Other Aromatic Heterocycles 1101
N- Sulfonyl Derivatives 1101
Carbamates 1105
N- Alkyl and N- Aryl Derivatives 1110
Amino Acetal Derivatives 1118
Amides 1122
Protection for the Amide ¿NH 1132
Amides 1132
Protection for the Sulfonamide ¿NH 1164
8. Protection for the Alkyne ¿CH 1177
9. Protection for the Phosphate Group 1185
Introduction 1188
Some General Methods for Phosphate Ester Formation 1190
Removal of Protective Groups from Phosphorus 1191
Alkyl Phosphates 1195
Phosphates Cleaved by Cyclodeesterification 1203
2- Substituted Ethyl Phosphates 1208
Haloethyl Phosphates 1215
Benzyl Phosphates 1218
Phenyl Phosphates 1224
Photochemically Cleaved Phosphate Protective Groups 1231
Amidates 1234
Miscellaneous Derivatives 1237
10. Protecting Group Effects in Carbohydrate Chemistry 1239
Introduction 1240
Early Observations Protecting Group- Induced Reactivity 1242
Relative Reactivities 1244
Fraser-Reid's Concept of Armed and Disarmed 1251
Examples of How Protecting Groups Arm and Disarm Glycosides 1252
Aglycone Transfer 1263
Participating Groups 1266
Ester at the C- 2 Hydroxyl 1266
Esters at Positions Other Than 2 1278
Ethers Primarily at the C- 2 Hydroxyl 1302
Conformational Restriction 1329
Benzylidene Group and other Acetals 1329
Directing Effect of Silylene Groups 1343
Carbonates as Conformational Restrictors 1364
Orthoester Conformational Restriction 1372
Silyl Groups: Conformational and Reactivity Effect 1376
Studies on the Conformational Flip Using Silyl Groups 1377
Amino Sugar Protection 1393
Imine Protection 1394
Protection of the NH2 as An Azide 1399
Imide Protection 1405
Oxazolidinones 1408
Introduction to the Formation of Sialyl Glycosides 1425
Amides and Their Effects 1429
Protecting Group Effects in the Glycosylation of 2- Deoxy Sugars 1446
Furanosides 1474
Protecting Group Effects on Acceptors 1494
C- Glycosylation 1522
Sphingolipids 1529
Introduction 1529
11. Reactivities Reagents and Reactivity Charts 1537
Reactivities 1537
Reagents 1538
Reactivity Charts 1540
Reactivity Chart 1. Protection for Hydroxyl Group: Ethers 1542
Reactivity Chart 2. Protection for Hydroxyl Group: Esters 1546
Reactivity Chart 3. Protection for 12- and 13- Diols 1550
Reactivity Chart 4. Protection for Phenols and Catechols 1554
Reactivity Chart 5. Protection for the Carbonyl Group 1558
Reactivity Chart 6. Protection for the Carboxyl Group 1562
Reactivity Chart 7. Protection for the Thiol Group 1566
Reactivity Chart 8. Protection for the Amino Group: Carbamates 1570
Reactivity Chart 9. Protection for the Amino Group: Amides 1574
Reactivity Chart 10. Protection for the Amino Group: Special ¿NH Protective Groups 1578
Reactivity Chart 11. Selective Deprotection of Silyl Ethers 1582
Index 1603
