Integral, reliable, and comprehensive guidance for chemists performing the complex syntheses required for the formation and cleavage of protective groups Organic synthesis is the preparation and creation of organic compounds for use in natural products, pharmaceuticals, and other molecules. The synthesis of molecules having multiple functional groups often requires the use of 'protective groups' to achieve site selectivity in a chemical reaction within a molecule bearing multiple sites of reactivity. Protective groups are installed temporarily to prevent unwanted reactions at a particular…mehr
Integral, reliable, and comprehensive guidance for chemists performing the complex syntheses required for the formation and cleavage of protective groups Organic synthesis is the preparation and creation of organic compounds for use in natural products, pharmaceuticals, and other molecules. The synthesis of molecules having multiple functional groups often requires the use of 'protective groups' to achieve site selectivity in a chemical reaction within a molecule bearing multiple sites of reactivity. Protective groups are installed temporarily to prevent unwanted reactions at a particular site, while transforming a different functional group. Once they have served their function, they are removed to expose the original group. Without a thorough understanding of the methods required to install and remove them, the design of a synthesis of a molecule having multiple functional groups in most cases is effectively impossible. Greene's Protective Groups in Organic Synthesis, 6th Edition is the definitive compilation of protective groups, their classification, and their application in a wide array of situations. With a long tradition of comprehensive coverage, organized on the basis of the functional group in need of protection and subsequent deprotection, it is an essential reference and resource for all chemists involved in organic syntheses. Now fully updated to reflect the current state of the art, it remains an indispensable resource for generating life-changing organic products. This edition contains a new chapter on how protective groups effect reactivity and selectivity in carbohydrate chemistry. Readers of the sixth edition of Greene's Protective Groups in Organic Synthesis will also find: * Methodology for planning selectivity in organic syntheses * Detailed discussion of all major functional groups including ethers, amides, and phenols * A discussion of the impact of protective groups on reactivity in carbohydrates Greene's Protective Groups in Organic Synthesis is ideal for synthetic organic chemists or medicinal chemists in academia, industry - pharmaceuticals, food, agrochemicals, and biotech - or government agencies.
Peter G. M. Wuts, PhD, is a renowned organic chemist, currently working as a chemistry consultant for both the biotech and the legal community. He continues a 50-year career in academia and the pharmaceutical industry.
Inhaltsangabe
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
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
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