Greene's Protective Groups in Organic Synthesis

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

• Preface to the Fifth Edition xiPreface to the Fourth Edition xiiiPreface to the Third Edition xvPreface to the Second Edition xviiPreface to the First Edition xixAbbreviations xxi1. The Role of Protective Groups in Organic Synthesis 1Properties of a Protective Group 1Historical Development 2Development of New Protective Groups 2Selection of a Protective Group from This Book 4Synthesis of Complex Substances: Two Examples (As used in the Synthesis of Himastatin and Palytoxin) of the Selection Introduction and Removal of Protective Groups 5Synthesis of Himastatin 5Synthesis of Palytoxin Carboxylic Acid 92. Protection for the Hydroxyl Group Including 12- and 13-Diols 17Ethers 26Substituted Methyl Ethers 33Substituted Ethyl Ethers 87Methoxy-Substituted Benzyl Ethers 146Silyl Ethers 201Esters 271Bisfluorous Chain-Type Propanoate (Bfp–OR) Ester 307Proximity-Assisted Deprotection for Ester Cleavage 329Miscellaneous Esters 336Sulfonates Sulfenates and Sulfinates as Protective Groups for Alcohols 337Carbonates 347Carbamates 371Protection for 12- and 13-Diols 375Monoprotection of Diols 375Cyclic Acetals and Ketals 385Chiral Ketones 446Cyclic Orthoesters 447Silyl Derivatives 456Cyclic Carbonates 465Cyclic Boronates 4683. Protection for Phenols and Catechols 472Protection for Phenols 475Ethers 475Silyl Ethers 522Esters 528Carbonates 535Carbamates 538Phosphinates 540Sulfonates 541Protection for Catechols (12-Dihydroxybenzenes) 545Cyclic Acetals and Ketals 545Cyclic Esters 551Protection for 2-Hydroxybenzenethiols 5524. Protection for the Carbonyl Group 554Acetals and Ketals 559Acyclic Acetals and Ketals 559Cyclic Acetals and Ketals 576Chiral Acetals and Ketals 611Dithio Acetals and Ketals 615Cyclic Dithio Acetals and Ketals 620Monothio Acetals and Ketals 644Diseleno Acetals and Ketals 649Miscellaneous Derivatives 650O-Substituted Cyanohydrins 650Substituted Hydrazones 654Oxime Derivatives 66112-Adducts to Aldehydes and Ketones 669Cyclic Derivatives 674Protection of the Carbonyl Group as Enolate Anions Enol Ethers Enamines and Imines 676Monoprotection of Dicarbonyl Compounds 679Selective Protection of α- and β-Diketones 679Cyclic Ketals Monothio and Dithio Ketals 6845. Protection for the Carboxyl Group 686Esters 692General Preparation of Esters 692General Cleavage of Esters 699Transesterification 704Enzymatically Cleavable Esters 711Substituted Methyl Esters 7232-Substituted Ethyl Esters 73926-Dialkylphenyl Esters 768Substituted Benzyl Esters 775Silyl Esters 792Activated Esters 796Miscellaneous Derivatives 799Stannyl Esters 812Amides and Hydrazides 812Amides 820Hydrazides 825Protection of Sulfonic Acids 828Protection of Boronic Acids 8316. Protection for the Thiol Group 837Thioethers 841S-Diphenylmethyl Substituted S-Diphenylmethyl and S-Triphenylmethyl Thioethers 855Substituted S-Methyl Derivatives: Monothio Dithio and Aminothio Acetals 864Substituted S-Ethyl Derivatives 875Silyl Thioethers 880Thioesters 881Thiocarbonate Derivatives 883Thiocarbamate Derivatives 885Miscellaneous Derivatives 886Unsymmetrical Disulfides 886Sulfenyl Derivatives 888Protection for Dithiols: Dithio Acetals and Ketals 891Protection for Sulfides 892S–P Derivatives 893Protection for the Amino Thiol Group 8947. Protection for the Amino Group 895Carbamates 907Substituted Ethyl Carbamates 921Carbamates Cleaved by a 16-Elimination 977Carbamates Cleaved by β-Elimination 979Photolytically Cleaved Carbamates 983Miscellaneous Carbamates 987Urea-Type Derivatives 989Amides 990Assisted Cleavage of Amides 1007Bisprotection of Amines 1009Special –Nh Protective Groups 1025N-Alkyl and N-Aryl Amines 1025Imine Derivatives 1060Enamine Derivatives 1069Quaternary Ammonium Salts 1072N-Heteroatom Derivatives 1073N-Metal Derivatives 1073N-N Derivatives 1078N-P Derivatives 1083N-Si Derivatives 1086N-S Derivatives 1088Protection of Amino Alcohols 1116Protection for Imidazoles Pyrroles Indoles and Other AromaticHeterocycles 1120N-Sulfonyl Derivatives 1120Carbamates 1124N-Alkyl and N-Aryl Derivatives 1129 N-Trialkylsilylamines R2N–SiR03 1131 N-Allylamine CH2.CHCH2NR2 1131N-Benzylamine (Bn–NR2) PhCH2–NR2 1132Amino Acetal Derivatives 1137Amides 1141Protection for the Amide –NH 1151Protection for the Sulfonamide –NH 11828. Protection for the Alkyne –CH 11949. Protection for the Phosphate Group 1203Some General Methods for Phosphate Ester Formation 1209Removal of Protective Groups from Phosphorus 1210Alkyl Phosphates 1214Phosphates Cleaved by Cyclodeesterification 12232-Substituted Ethyl Phosphates 1228Haloethyl Phosphates 1236Benzyl Phosphates 1239Phenyl Phosphates 1246Photochemically Cleaved Phosphate Protective Groups 1254Amidates 1258Miscellaneous Derivatives 126110. Reactivities Reagents and Reactivity Charts 1263Reactivities 1263Reagents 1264Reactivity Charts 1267Reactivity Chart 1. Protection for Hydroxyl Group: Ethers 1269Reactivity Chart 2. Protection for Hydroxyl Group: Esters 1274Reactivity Chart 3. Protection for 12- and 13-Diols 1278Reactivity Chart 4. Protection for Phenols and Catechols 1282Reactivity Chart 5. Protection for the Carbonyl Group 1286Reactivity Chart 6. Protection for the Carboxyl Group 1290Reactivity Chart 7. Protection for the Thiol Group 1294Reactivity Chart 8. Protection for the Amino Group: Carbamates 1298Reactivity Chart 9. Protection for the Amino Group: Amides 1302Reactivity Chart 10. Protection for the Amino Group: Special –NH Protective Groups 1306Reactivity Chart 11. Selective Deprotection of Silyl Ethers 1311Index 1333