Greene's Protective Groups in Organic Synthesis

An indispensable reference for any practicing synthetic organic or medicinal chemist, this book continues the tradition of Greene’s as comprehensive in the overall scope of coverage, providing the most relevant and useful examples to illustrate each methodology. • Presents valuable material, on the application of protective groups in organic chemistry, that is not easily found by casual searching • Helps chemists to plan, investigate, and carry out organic syntheses in an efficient manner • Adds over 2800 new references to update since the publication of the last edition • Reviews of the prior edition: "An essential bible for the library or personal bookshelf of chemists performing complex synthesis." (CHOICE, May 2007) "...the most up-to-date compilation available...should be an integral part of all institutional libraries...it is also highly recommended that individuals...maintain their own copy..." (Journal of Medicinal Chemistry, March 8, 2007) "...continues to be a comprehensive guide to the techniques for the formation and cleavage of protective groups." (Journal of the American Chemical Society, January 31, 2007)

Table of Contents:
Preface to the Fifth Edition xi Preface to the Fourth Edition xiii Preface to the Third Edition xv Preface to the Second Edition xvii Preface to the First Edition xix Abbreviations xxi 1. The Role of Protective Groups in Organic Synthesis 1 Properties of a Protective Group 1 Historical Development 2 Development of New Protective Groups 2 Selection of a Protective Group from This Book 4 Synthesis of Complex Substances: Two Examples (As used in the Synthesis of Himastatin and Palytoxin) of the Selection Introduction and Removal of Protective Groups 5 Synthesis of Himastatin 5 Synthesis of Palytoxin Carboxylic Acid 9 2. Protection for the Hydroxyl Group Including 12- and 13-Diols 17 Ethers 26 Substituted Methyl Ethers 33 Substituted Ethyl Ethers 87 Methoxy-Substituted Benzyl Ethers 146 Silyl Ethers 201 Esters 271 Bisfluorous Chain-Type Propanoate (Bfp–OR) Ester 307 Proximity-Assisted Deprotection for Ester Cleavage 329 Miscellaneous Esters 336 Sulfonates Sulfenates and Sulfinates as Protective Groups for Alcohols 337 Carbonates 347 Carbamates 371 Protection for 12- and 13-Diols 375 Monoprotection of Diols 375 Cyclic Acetals and Ketals 385 Chiral Ketones 446 Cyclic Orthoesters 447 Silyl Derivatives 456 Cyclic Carbonates 465 Cyclic Boronates 468 3. Protection for Phenols and Catechols 472 Protection for Phenols 475 Ethers 475 Silyl Ethers 522 Esters 528 Carbonates 535 Carbamates 538 Phosphinates 540 Sulfonates 541 Protection for Catechols (12-Dihydroxybenzenes) 545 Cyclic Acetals and Ketals 545 Cyclic Esters 551 Protection for 2-Hydroxybenzenethiols 552 4. Protection for the Carbonyl Group 554 Acetals and Ketals 559 Acyclic Acetals and Ketals 559 Cyclic Acetals and Ketals 576 Chiral Acetals and Ketals 611 Dithio Acetals and Ketals 615 Cyclic Dithio Acetals and Ketals 620 Monothio Acetals and Ketals 644 Diseleno Acetals and Ketals 649 Miscellaneous Derivatives 650 O-Substituted Cyanohydrins 650 Substituted Hydrazones 654 Oxime Derivatives 661 12-Adducts to Aldehydes and Ketones 669 Cyclic Derivatives 674 Protection of the Carbonyl Group as Enolate Anions Enol Ethers Enamines and Imines 676 Monoprotection of Dicarbonyl Compounds 679 Selective Protection of α- and β-Diketones 679 Cyclic Ketals Monothio and Dithio Ketals 684 5. Protection for the Carboxyl Group 686 Esters 692 General Preparation of Esters 692 General Cleavage of Esters 699 Transesterification 704 Enzymatically Cleavable Esters 711 Substituted Methyl Esters 723 2-Substituted Ethyl Esters 739 26-Dialkylphenyl Esters 768 Substituted Benzyl Esters 775 Silyl Esters 792 Activated Esters 796 Miscellaneous Derivatives 799 Stannyl Esters 812 Amides and Hydrazides 812 Amides 820 Hydrazides 825 Protection of Sulfonic Acids 828 Protection of Boronic Acids 831 6. Protection for the Thiol Group 837 Thioethers 841 S-Diphenylmethyl Substituted S-Diphenylmethyl and S-Triphenylmethyl Thioethers 855 Substituted S-Methyl Derivatives: Monothio Dithio and Aminothio Acetals 864 Substituted S-Ethyl Derivatives 875 Silyl Thioethers 880 Thioesters 881 Thiocarbonate Derivatives 883 Thiocarbamate Derivatives 885 Miscellaneous Derivatives 886 Unsymmetrical Disulfides 886 Sulfenyl Derivatives 888 Protection for Dithiols: Dithio Acetals and Ketals 891 Protection for Sulfides 892 S–P Derivatives 893 Protection for the Amino Thiol Group 894 7. Protection for the Amino Group 895 Carbamates 907 Substituted Ethyl Carbamates 921 Carbamates Cleaved by a 16-Elimination 977 Carbamates Cleaved by β-Elimination 979 Photolytically Cleaved Carbamates 983 Miscellaneous Carbamates 987 Urea-Type Derivatives 989 Amides 990 Assisted Cleavage of Amides 1007 Bisprotection of Amines 1009 Special –Nh Protective Groups 1025 N-Alkyl and N-Aryl Amines 1025 Imine Derivatives 1060 Enamine Derivatives 1069 Quaternary Ammonium Salts 1072 N-Heteroatom Derivatives 1073 N-Metal Derivatives 1073 N-N Derivatives 1078 N-P Derivatives 1083 N-Si Derivatives 1086 N-S Derivatives 1088 Protection of Amino Alcohols 1116 Protection for Imidazoles Pyrroles Indoles and Other Aromatic Heterocycles 1120 N-Sulfonyl Derivatives 1120 Carbamates 1124 N-Alkyl and N-Aryl Derivatives 1129 N-Trialkylsilylamines R2N–SiR03 1131 N-Allylamine CH2.CHCH2NR2 1131 N-Benzylamine (Bn–NR2) PhCH2–NR2 1132 Amino Acetal Derivatives 1137 Amides 1141 Protection for the Amide –NH 1151 Protection for the Sulfonamide –NH 1182 8. Protection for the Alkyne –CH 1194 9. Protection for the Phosphate Group 1203 Some General Methods for Phosphate Ester Formation 1209 Removal of Protective Groups from Phosphorus 1210 Alkyl Phosphates 1214 Phosphates Cleaved by Cyclodeesterification 1223 2-Substituted Ethyl Phosphates 1228 Haloethyl Phosphates 1236 Benzyl Phosphates 1239 Phenyl Phosphates 1246 Photochemically Cleaved Phosphate Protective Groups 1254 Amidates 1258 Miscellaneous Derivatives 1261 10. Reactivities Reagents and Reactivity Charts 1263 Reactivities 1263 Reagents 1264 Reactivity Charts 1267 Reactivity Chart 1. Protection for Hydroxyl Group: Ethers 1269 Reactivity Chart 2. Protection for Hydroxyl Group: Esters 1274 Reactivity Chart 3. Protection for 12- and 13-Diols 1278 Reactivity Chart 4. Protection for Phenols and Catechols 1282 Reactivity Chart 5. Protection for the Carbonyl Group 1286 Reactivity Chart 6. Protection for the Carboxyl Group 1290 Reactivity Chart 7. Protection for the Thiol Group 1294 Reactivity Chart 8. Protection for the Amino Group: Carbamates 1298 Reactivity Chart 9. Protection for the Amino Group: Amides 1302 Reactivity Chart 10. Protection for the Amino Group: Special –NH Protective Groups 1306 Reactivity Chart 11. Selective Deprotection of Silyl Ethers 1311 Index 1333

About the Author :
Peter G.M. Wuts is a Distinguished Scientist at Kalexsyn, Inc. in Kalamazoo, Michigan.

Review :
"An essential bible for the library or personal bookshelf of chemists performing complex synthesis." ("CHOICE", May 2007)."..the most up-to-date compilation available...should be an integral part of all institutional libraries...it is also highly recommended that individuals...maintain their own copy..." ("Journal of Medicinal Chemistry", March 8, 2007) ."..continues to be a comprehensive guide to the techniques for the formation and cleavage of protective groups." ("Journal of the American Chemical Society", January 31, 2007) , .."the most up-to-date compilation available...should be an integral part of all institutional libraries...it is also highly recommended that individuals...maintain their own copy..." ("Journal of Medicinal Chemistry", March 8, 2007) , .."continues to be a comprehensive guide to the techniques for the formation and cleavage of protective groups." ("Journal of the American Chemical Society", January 31, 2007) .,."the most up-to-date compilation available...should be an integral part of all institutional libraries...it is also highly recommended that individuals...maintain their own copy..." ("Journal of Medicinal Chemistry," March 8, 2007) .,."continues to be a comprehensive guide to the techniques for the formation and cleavage of protective groups." ("Journal of the American Chemical Society," January 31, 2007)