Preface to the Student	6
	Preface to the Instructor	10
	Contents	14
	1 The Basics	18
	1.1 Structure and Stability of Organic Compounds	18
	1.1.1 Conventions of Drawing Structures	18
	1.1.2 Lewis Structures	20
	1.1.3 Molecular Shape	26
	1.1.4 Aromaticity	30
	1.2 Brønsted Acidity and Basicity	33
	1.2.1 pKa Values	33
	1.2.2 Tautomerism	36
	1.3 Kinetics and Thermodynamics	37
	1.4 Getting Started in Drawing a Mechanism	39
	1.5 Classes of Overall Transformations	42
	1.6 Classes of Mechanisms	43
	1.6.1 Polar Mechanisms	44
	1.6.2 Free-Radical Mechanisms	55
	1.6.3 Pericyclic Mechanisms	58
	1.6.4 Transition-Metal-Catalyzed and Mediated Mechanisms	59
	1.7 Summary	59
	PROBLEMS	60
	2 Polar Reactions under Basic Conditions	67
	2.1 Substitution and Elimination at C(sp3)–X Bonds, Part I	67
	2.1.1 Substitution by the SN2 Mechanism	68
	2.1.2 -Elimination by the E2 and E1cb Mechanisms	70
	2.1.3 Predicting Substitution vs. Elimination	73
	2.2 Addition of Nucleophiles to Electrophilic Bonds	75
	2.2.1 Addition to Carbonyl Compounds	75
	2.2.2 Conjugate Addition	84
	2.3 Substitution at C(sp2)–X Bonds	86
	2.3.1 Substitution at Carbonyl C	86
	2.3.2 Substitution at Alkenyl and Aryl C	91
	2.3.3 Metal Insertion	95
	2.4 Substitution and Elimination at C(sp3)–X Bonds, Part II	97
	2.4.1 Substitution by the SRN1 Mechanism	97
	2.4.2 Substitution by the Elimination–Addition Mechanism	98
	2.4.3 Substitution by the One-Electron Transfer Mechanism	99
	2.4.4 Metal Insertion	100
	2.4.5 -Elimination	101
	2.5 Base-Promoted Rearrangements	104
	2.5.1 Migration from C to C	105
	2.5.2 Migration from C to O or N	107
	2.5.3 Migration from B to C or O	108
	2.6 Two Multistep Reactions	109
	2.6.1 The Swern Oxidation	109
	2.6.2 The Mitsunobu Reaction	111
	2.7 Summary	112
	PROBLEMS	114
	3 Polar Reactions under Acidic Conditions	122
	3.1 Carbocations	122
	3.1.1 Carbocation Stability	123
	3.1.2 Carbocation Generation	126
	3.1.3 Typical Reactions of Carbocations	129
	3.2 Substitution and -Elimination Reactions at C(sp3)–X	134
	3.2.1 Substitution by the SN1 and SN2 Mechanisms	134
	3.2.2 -Elimination by the E1 Mechanism	137
	3.2.3 Predicting Substitution vs. Elimination	139
	3.3 Electrophilic Addition to Nucleophilic C––C Bonds	139
	3.4 Substitution at Nucleophilic C –C Bonds	142
	3.4.1 Electrophilic Aromatic Substitution	142
	3.4.2 Aromatic Substitution of Anilines via Diazonium Salts	146
	3.4.3 Electrophilic Aliphatic Substitution	148
	3.5 Nucleophilic Addition to and Substitution at Electrophilic Bonds	149
	3.5.1 Heteroatom Nucleophiles	149
	3.5.2 Carbon Nucleophiles	153
	3.6 Summary	157
	PROBLEMS	158
	4 Pericyclic Reactions	165
	4.1 Introduction	165
	4.1.1 Classes of Pericyclic Reactions	165
	4.1.2 Polyene MOs	171
	4.2 Electrocyclic Reactions	173
	4.2.1 Typical Reactions	173
	4.2.2 Stereospecificity	180
	4.2.3 Stereoselectivity	185
	4.3 Cycloadditions	187
	4.3.1 Typical Reactions	187
	4.3.2 Regioselectivity	200
	4.3.3 Stereospecificity	201
	4.3.4 Stereoselectivity	208
	4.4 Sigmatropic Rearrangements	212
	4.4.1 Typical Reactions	212
	4.4.2 Stereospecificity	218
	4.4.3 Stereoselectivity	223
	4.5 Ene Reactions	227
	4.6 Summary	230
	PROBLEMS	232
	5 Free-Radical Reactions	241
	5.1 Free Radicals	241
	5.1.1 Stability	241
	5.1.2 Generation from Closed-Shell Species	244
	5.1.3 Typical Reactions	249
	5.1.4 Chain vs. Nonchain Mechanisms	255
	5.2 Chain Free-Radical Reactions	256
	5.2.1 Substitution Reactions	256
	5.2.2 Addition and Fragmentation Reactions	261
	5.3 Nonchain Free-Radical Reactions	269
	5.3.1 Photochemical Reactions	269
	5.3.2 Reductions and Oxidations with Metals	271
	5.3.3 Cycloaromatizations	278
	5.4 Miscellaneous Radical Reactions	278
	5.4.1 1,2-Anionic Rearrangements	278
	5.4.2 Triplet Carbenes and Nitrenes	279
	5.5 Summary	281
	PROBLEMS	281
	6 Transition-Metal-Catalyzed and -Mediated Reactions	287
	6.1 Introduction to the Chemistry of Transition Metals	287
	6.1.1. Conventions of Drawing Structures	287
	6.1.2 Counting Electrons	288
	6.1.3 Typical Reactions	293
	6.1.4. Stoichiometric vs. Catalytic Mechanisms	299
	6.2 Addition Reactions	300
	6.2.1 Late-Metal-Catalyzed Hydrogenation and Hydrometallation (Pd, Pt, Rh)	300
	6.2.2 Hydroformylation (Co, Rh)	303
	6.2.3 Hydrozirconation (Zr)	304
	6.2.4 Alkene Polymerization (Ti, Zr, Sc, and Others)	305
	6.2.5 Cyclopropanation, Epoxidation, and Aziridination of Alkenes (Cu, Rh, Mn, Ti)	307
	6.2.6 Dihydroxylation and Aminohydroxylation of Alkenes (Os)	309
	6.2.7 Nucleophilic Addition to Alkenes and Alkynes (Hg, Pd)	311
	6.2.8 Conjugate Addition Reactions (Cu)	314
	6.2.9 Reductive Coupling Reactions (Ti, Zr)	314
	6.2.10 Pauson–Khand Reaction (Co)	318
	6.2.11 Dötz Reaction (Cr)	320
	6.2.12 Metal-Catalyzed Cycloaddition and Cyclotrimerization (Co, Ni, Rh)	323
	6.3 Substitution Reactions	326
	6.3.1 Hydrogenolysis (Pd)	326
	6.3.2 Carbonylation of Alkyl Halides (Pd, Rh)	328
	6.3.3 Heck Reaction (Pd)	330
	6.3.4 Coupling Reactions Between Nucleophiles and C(sp2)–X: Kumada, Stille, Suzuki, Negishi, Buchwald–Hartwig, Sonogashira, and Ullmann Reactions (Ni, Pd, Cu)	331
	6.3.5 Allylic Substitution (Pd)	335
	6.3.6 Palladium-Catalyzed Nucleophilic Substitution of Alkenes	336
	6.3.7 Tebbe Reaction (Ti)	338
	6.3.8 Propargyl Substitution in Cobalt–Alkyne Complexes	339
	6.4 Rearrangement Reactions	340
	6.4.1 Alkene Isomerization (Rh)	340
	6.4.2 Olefin and Alkyne Metathesis (Ru, W, Mo, Ti)	340
	6.5 Elimination Reactions	343
	6.5.1 Oxidation of Alcohols (Cr, Ru)	343
	6.5.2 Decarbonylation of Aldehydes (Rh)	343
	6.6 Summary	344
	PROBLEMS	345
	7 Mixed-Mechanism Problems	351
	A Final Word	356
	Index	358
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