ORGANIC REACTION MECHANISMS: PRINCIPLES AND PRACTICE
CONTENTS THE BASICS STRUCTURE AND STABILITY OF ORGANIC COMPOUNDS CONVENTIONS OF DRAWING STRUCTURES; GROSSMAN’S RULE LEWIS STRUCTURES; RESONANCE STRUCTURES MOLECULAR SHAPE; HYBRIDIZATION AROMATICITY BRØNSTED ACIDITY AND BASICITY PKA VALUES TAUTOMERISM KINETICS AND THERMODYNAMICS GETTING STARTED IN DRAWING A MECHANISM CLASSES OF OVERALL TRANSFORMATIONS CLASSES OF MECHANISMS POLAR MECHANISMS FREE-RADICAL MECHANISMS PERICYCLIC MECHANISMS TRANSITION-METAL-CATALYZED AND -MEDIATED MECHANISMS SUMMARY PROBLEMS POLAR REACTIONS UNDER BASIC CONDITIONS SUBSTITUTION AND ELIMINATION AT C(SP3)–X BONDS, PART I SUBSTITUTION BY THE SN2 MECHANISM ELIMINATION BY THE E2 AND E1CB MECHANISMS PREDICTING SUBSTITUTION VS ELIMINATION ADDITION OF NUCLEOPHILES TO ELECTROPHILIC BONDS ADDITION TO CARBONYL COMPOUNDS CONJUGATE ADDITION; THE MICHAEL REACTION SUBSTITUTION AT C(SP2)–X BONDS SUBSTITUTION AT CARBONYL C SUBSTITUTION AT ALKENYL AND ARYL C METAL INSERTION; HALOGEN–METAL EXCHANGE SUBSTITUTION AND ELIMINATION AT C(SP3)–X BONDS, PART II SUBSTITUTION BY THE SRN1 MECHANISM SUBSTITUTION BY THE ELIMINATION–ADDITION MECHANISM SUBSTITUTION BY THE ONE-ELECTRON TRANSFER MECHANISM ELIMINATION; GENERATION AND REACTIONS OF CARBENES BASE-PROMOTED REARRANGEMENTS MIGRATION FROM C TO C MIGRATION FROM C TO O OR N MIGRATION FROM B TO C OR O TWO MULTISTEP REACTIONS THE SWERN OXIDATION THE MITSUNOBU REACTION POLAR REACTIONS UNDER ACIDIC CONDITIONS CARBOCATIONS CARBOCATION STABILITY CARBOCATION GENERATION; THE ROLE OF PROTONATION TYPICAL REACTIONS OF CARBOCATIONS; REARRANGEMENTS SUBSTITUTION AND -ELIMINATION REACTIONS AT C(SP3)–X SUBSTITUTION BY THE SN1 AND SN2 MECHANISMS ELIMINATION BY THE E1 MECHANISM ELECTROPHILIC ADDITION TO NUCLEOPHILIC C––C BONDS SUBSTITUTION AT NUCLEOPHILIC C––C BONDS ELECTROPHILIC AROMATIC SUBSTITUTION AROMATIC SUBSTITUTION OF ANILINES VIA DIAZONIUM SALTS ELECTROPHILIC ALIPHATIC SUBSTITUTION NUCLEOPHILIC ADDITION TO AND SUBSTITUTION AT ELECTROPHILIC BONDS HETEROATOM NUCLEOPHILES CARBON NUCLEOPHILES PERICYCLIC REACTIONS INTRODUCTION CLASSES OF PERICYCLIC REACTIONS POLYENE MOS ELECTROCYCLIC REACTIONS TYPICAL REACTIONS STEREOSPECIFICITY STEREOSELECTIVITY CYCLOADDITIONS REGIOSELECTIVITY SIGMATROPIC REARRANGEMENTS ENE REACTIONS FREE-RADICAL REACTIONS FREE RADICALS STABILITY GENERATION FROM CLOSED-SHELL SPECIES CHAIN VS NONCHAIN MECHANISMS CHAIN FREE-RADICAL REACTIONS SUBSTITUTION REACTIONS ADDITION AND FRAGMENTATION REACTIONS NONCHAIN FREE-RADICAL REACTIONS PHOTOCHEMICAL REACTIONS REDUCTIONS AND OXIDATIONS WITH METALS CYCLOAROMATIZATIONS MISCELLANEOUS RADICAL REACTIONS 1,2-ANIONIC REARRANGEMENTS; LONE-PAIR INVERSION TRIPLET CARBENES AND NITRENES TRANSITION-METAL-MEDIATED AND -CATALYZED REACTIONS INTRODUCTION TO THE CHEMISTRY OF TRANSITION METALS CONVENTIONS OF DRAWING STRUCTURES COUNTING ELECTRONS STOICHIOMETRIC VS CATALYTIC MECHANISMS ADDITION REACTIONS LATE-METAL-CATALYZED HYDROGENATION AND HYDROMETALLATION (PD, PT, RH) HYDROFORMYLATION (CO, RH) HYDROZIRCONATION (ZR) ALKENE POLYMERIZATION (TI, ZR, SC, AND OTHERS) CYCLOPROPANATION, EPOXIDATION, AND AZIRIDINATION OF ALKENES (CU, RH, MN, TI) DIHYDROXYLATION AND AMINOHYDROXYLATION OF ALKENES (OS) NUCLEOPHILIC ADDITION TO ALKENES AND ALKYNES (HG, PD) CONJUGATE ADDITION REACTIONS (CU) REDUCTIVE COUPLING REACTIONS (TI, ZR) PAUSON–KHAND REACTION (CO) DÖTZ REACTION (CR) METAL-CATALYZED CYCLOADDITION AND CYCLOTRIMERIZATION (CO, NI, RH) HYDROGENOLYSIS (PD) CARBONYLATION OF ALKYL HALIDES (PD, RH) HECK REACTION (PD) COUPLING REACTIONS BETWEEN NUCLEOPHILES AND C(SP2)–X: KUMADA, STILLE, SUZUKI, NEGISHI, BUCHWALD–HARTWIG, SONOGASHIRA, AND ULLMANN REACTIONS (NI, PD, CU) ALLYLIC SUBSTITUTION (PD) PD-CATALYZED NUCLEOPHILIC SUBSTITUTION OF ALKENES; WACKER OXIDATION TEBBE REACTION (TI) PROPARGYL SUBSTITUTION IN CO–ALKYNE COMPLEXES REARRANGEMENT REACTIONS ALKENE ISOMERIZATION (RH) OLEFIN AND ALKYNE METATHESIS (RU, W, MO, TI) ELIMINATION REACTIONS OXIDATION OF ALCOHOLS (CR, RU) DECARBONYLATION OF ALDEHYDES (RH) MIXED-MECHANISM PROBLEMS CONVENTIONS OF DRAWING STRUCTURES; GROSSMAN’S RULE WHEN ORGANIC STRUCTURES ARE DRAWN, THE H ATOMS ATTACHED TO C ARE USUALLY OMIT- TED (ON THE OTHER HAND, H ATOMS ATTACHED TO HETEROATOMS ARE ALWAYS SHOWN ) IT IS EXTREMELY IMPORTANT FOR YOU NOT TO FORGET THAT THEY ARE THERE! COMMON ERROR ALERT: DON’T LOSE TRACK OF THE UNDRAWN H ATOMS THERE ARE BIG DIFFERENCES AMONG ISOBUTANE, THE T-BUTYL RADICAL, AND THE T-BUTYL CATION, BUT IF YOU LOSE TRACK OF YOUR H ATOMS YOU MIGHT CONFUSE THE TWO FOR THIS REASON, I HAVE FORMULATED WHAT I MODESTLY CALL GROSSMAN’S RULE: ALWAYS DRAW ALL BONDS AND H3C H3C H