PRINCIPLES OF GENERAL ORGANIC CHEMISTRY

By CHARLOTTE HARRIS

CONTENTS OF PART B CHAPTER 1 ALKYLATION OF NUCLEOPHILIC CARBON INTERMEDIATES 11 GENERATION OF CARBANIONS BY DEPROTONATION 12 REGIOSELECTIVITY AND STEREOSELECTIVITY IN ENOLATE FORMATION 13 OTHER MEANS OF GENERATING ENOLATES 14 ALKYLATION OF ENOLATES 15 GENERATION AND ALKYLATION OF DIANIONS 16 MEDIUM EFFECTS IN THE ALKYLATION OF ENOLATES 17 OXYGEN VERSUS CARBON AS THE SITE OF ALKYLATION 18 ALKYLATION OF ALDEHYDES, ESTERS, AMIDES, AND NITRILES 19 THE NITROGEN ANALOGS OF ENOLS AND ENOLATES-ENAMINES AND IMINE ANIONS 110 ALKYLATION OF CARBON NUCLEOPHILES BY CONJUGATE ADDITION GENERAL REFERENCES PROBLEMS 1 5 10 11 2022 23 24 31 39 47 47 24 THE WITTIG AND RELATED REACTIONS OF PHOSPHORUS-STABILIZED CARBON NUCLEOPHILES CONTENTS OF PART B 25 REACTIONS OF CARBONYL COMPOUNDS WITH A-TRIMETHYLSILYLCARBANIONS 26 SULFUR YLIDES AND RELATED NUCLEOPHILES 27 NUCLEOPHILIC ADDITION-CYCLIZATION GENERAL REFERENCES PROBLEMS CHAPTER 3 FUNCTIONAL GROUP INTERCONVERSION BY NUCLEOPHILIC SUBSTITUTION 31 CONVERSION OF ALCOHOLS TO ALKYLATING AGENTS 311 SULFONATE ESTERS 312 HALIDES, 32 INTRODUCTION OF FUNCTIONAL GROUPS BY NUCLEOPHILIC SUBSTITUTION AT SATURATED CARBON 321 GENERAL SOLVENT EFFECTS 322 NITRILES 323 AZIDES 324 OXYGEN NUCLEOPHILES 325 NITROGEN NUCLEOPHILES 326 SULFUR NUCLEOPHILES 327 PHOSPHORUS NUCLEOPHILES 328 SUMMARY OF NUCLEOPHILIC SUBSTITUTION AT SATURATED CARBON 33 NUCLEOPHILIC CLEAVAGE OF CARBON-OXYGEN BONDS IN ETHERS AND ESTERS 34 INTERCONVERSION OF CARBOXYLIC ACID DERIVATIVES 341 PREPARATION OF REACTIVE REAGENTS FOR ACYLATION 342 PREPARATION OF ESTERS 343 PREPARATION OF AMIDES PROBLEMS 111 120 122 127 128 128 141 141 141 142 147 147 150 150 152 155 158 158 159 159 164 166 172 172 180 CHAPTER 4 ELECTROPHILIC ADDITIONS TO CARBON-CARBON MULTIPLE BONDS 191 41 ADDITION OF HYDROGEN HALIDES 191 CHAPTER 2 REACTION OF CARBON NUCLEOPHILES WITH CARBONYL GROUPS 21 ALDOL ADDITION AND CONDENSATION REACTIONS 42 HYDRATION AND OTHER ACID-CATALYZED ADDITIONS OF OXYGEN NUCLEOPHILES 195 57 43 OXYMERCURATION 196 57 44 ADDITION OF HALOGENS TO ALKENES 200 211 THE GENERAL MECHANISM 57 45 ELECTROPHILIC SULFUR AND SELENIUM REAGENTS 209 212 MIXED ALDOL CONDENSATIONS WITH AROMATIC ALDEHYDES 60 46 ADDITION OF OTHER ELECTROPHILIC REAGENTS 216 213 CONTROL OF REGIOCHEMISTRY AND STERCOCHEMISTRY OF MIXED ALDOL 47 ELECTROPHILIC SUBSTITUTION ALPHA TO CARBONYL GROUPS 216 REACTIONS OF ALIPHATIC ALDEHYDES AND KETONES 62 48 ADDITIONS TO ALLENES AND ALKYNES 222 214 INTRAMOLECULAR ALDOL REACTIONS AND THE ROBINSON ANNULATION 89 49 ADDITION AT DOUBLE BONDS VIA ORGANOBORANE INTERMEDIATES 226 22 ADDITION REACTIONS OF IMINES AND IMINIUM IONS 96 491 HYDROBORATION 226 221 THE MANNICH REACTION 222 AMINE-CATALYZED CONDENSATION REACTIONS 23 ACYLATION OF CARBANIONS 96 492 REACTIONS OF ORGANOBORANES 232 100 493 ENANTIOSELECTIVE HYDROBORATION 236 101 494 HYDROBORATION OF ALKYNES 239 ACTIVATE WINDOWS GENERAL REFERENCES PROBLEMS CHAPTER 5 REDUCTION OF CARBONYL AND OTHER FUNCTIONAL GROUPS 249 51 ADDITION OF HYDROGEN 249 511 CATALYTIC HYDROGENATION 249 512 OTHER HYDROGEN-TRANSFER REAGENTS 262 52 GROUP III HYDRIDE-DONOR REAGENTS 262 521 REDUCTION OF CARBONYL COMPOUNDS 262 522 STEREOSELECTIVITY OF HYDRIDE REDUCTION 273 213 523 REDUCTION OF OTHER FUNCTIONAL GROUPS BY HYDRIDE DONO 280 53 GROUP IV HYDRIDE DONORS 286 54 HYDROGEN-ATOM DONORS 288 55 DISSOLVING-METAL REDUCTIONS 290 551 ADDITION OF HYDROGEN 292 552 REDUCTIVE REMOVAL OF FUNCTIONAL GROUPS 296 553 REDUCTIVE CARBON-CARBON BOND FORMATION 299 56 REDUCTIVE DEOXYGENATION OF CARBONYL GROUPS 307 57 REDUCTIVE ELIMINATION AND FRAGMENTATION 310 GENERAL REFERENCES 315 PROBLEMS 316 240 CHAPTER 7 ORGANOMETALLIC COMPOUNDS OF THE GROUP I, II, AND III METALS 433 241 CONTENTS OF PART B CONTENTS OF PART B 71 PREPARATION AND PROPERTIES 433 72 REACTIONS OF ORGANOMAGNESIUM AND ORGANOLITHIUM COMPOUNDS 445 721 REACTIONS WITH ALKYLATING AGENTS 445 722 REACTIONS WITH CARBONYL COMPOUNDS 446 73 458 ORGANIC DERIVATIVES OF GROUP IIB AND GROUP IIIB METALS 731 ORGANOZINC COMPOUNDS 459 732 ORGANOCADMIUM COMPOUNDS 463 733 ORGANOMERCURY COMPOUNDS 464 734 ORGANOINDIUM REAGENTS 74 ORGANOLANTHANIDE REAGENTS 467 GENERAL REFERENCES PROBLEMS 465 468 468 61 CYCLOADDITION REACTIONS CHAPTER 6 CYCLOADDITIONS, UNIMOLECULAR REARRANGEMENTS, AND THERMAL ELIMINATIONS 611 THE DIELS-ALDER REACTION: GENERAL FEATURES 331 331 332 612 THE DIELS-ALDER REACTION: DIENOPHILES 339 CHAPTER & REACTIONS INVOLVING THE TRANSITION METALS 81 ORGANOCOPPER INTERMEDIATES 811 PREPARATION AND STRUCTURE OF ORGANOCOPPER REAGENTS 812 REACTIONS INVOLVING ORGANOCOPPER REAGENTS AND INTERMEDIATES 82 REACTIONS INVOLVING ORGANOPALLADIUM INTERMEDIATES 821 PALLADIUM-CATALYZED NUCLEOPHILIC SUBSTITUTION AND ALKYLATION 822 THE HOCK REACTION 823 PALLADIUM-CATALYZED CROSS COUPLING 824 CARBONYLATION REACTIONS 83 REACTIONS INVOLVING ORGANONICKEL COMPOUNDS 84 REACTIONS INVOLVING RHODIUM AND COBALT 529 85 ORGANOMETALLIC COMPOUNDS WITH A BONDING GENERAL REFERENCES PROBLEMS 477 477 477 481 499 501 503 507 521 525 531 535 536 613 THE DIELS-ALDER REACTION: DIENES 345 614 ASYMMETRIC DIELS-ALDER REACTIONS 349 615 INTRAMOLECULAR DIELS-ALDER REACTIONS 353 359 62 DIPOLAR CYCLOADDITION REACTIONS CHAPTER 9 CARBON-CARBON BOND-FORMING REACTIONS OF COMPOUNDS OF BORON, SILICON, AND TIN 63 [2+2] CYCLOADDITIONS AND OTHER REACTIONS LEADING TO CYCLOBUTANES 367 547 64 PHOTOCHEMICAL CYCLOADDITION REACTIONS 370 65 [3,3] SIGMATROPIC REARRANGEMENTS 376 651 COPE REARRANGEMENTS 376 91 ORGANOBORON COMPOUNDS 547 911 SYNTHESIS OF ORGANOBORANES 547 652 CLAISEN REARRANGEMENTS 383 912 CARBON-CARBON BOND-FORMING REACTIONS OF ORGANOBORANES 549 66 [2,3] SIGMATROPIC REARRANGEMENTS 394 92 ORGANOSILICON COMPOUNDS 563 67 ENE REACTIONS 399 921 SYNTHESIS OF ORGANOSILANES 563 68 UNIMOLECULAR THERMAL ELIMINATION REACTIONS 403 922 CARBON-CARBON BOND-FORMING REACTIONS 567 681 CHELETROPIC ELIMINATION 403 93 ORGANOTIN COMPOUNDS 576 682 DECOMPOSITION OF CYCLIC AZO COMPOUNDS 405 931 SYNTHESIS OF ORGANOSTANNANES 576 683 ELIMINATIONS INVOLVING CYCLIC TRANSITION STATES 408 932 CARBON-CARBON BOND-FORMING REACTIONS 579 585 GENERAL REFERENCES 414 GENERAL REFERENCES PROBLEMS 414 PROBLEMS 586 ACTIVATE WINDOWS