March's Advanced Organic Chemistry	3
	Contents	7
	New Reaction Sections Correlation: 7th edition ? 8th edition	17
	7th ? 8th	17
	Preface	23
	Common Abbreviations	27
	Biographical Statement	33
	New Features of the 8th Edition	35
	PART I INTRODUCTION	37
	1 Localized Chemical Bonding	39
	1.A Covalent Bonding	39
	1.B Multiple Valence	43
	1.C Hybridization	43
	1.D Multiple Bonds	45
	1.E Photoelectron Spectroscopy	48
	1.F Electronic Structures of Molecules	51
	1.G Electronegativity	53
	1.H Dipole Moment	55
	1.I Inductive and Field Effects	56
	1.J Bond Distances	59
	1.K Bond Angles	63
	1.L Bond Energies	65
	2 Delocalized Chemical Bonding	69
	2.A Molecular Orbitals	70
	2.B Bond Energies and Distances in Compounds Containing Delocalized Bonds	73
	2.C Molecules that have Delocalized Bonds	75
	2.D Cross Conjugation	80
	2.E The Rules of Resonance	82
	2.F The Resonance Effect	84
	2.G Steric Inhibition of Resonance and the Influences of Strain	84
	2.H p??????–d?????? Bonding: Ylids	88
	2.I Aromaticity	90
	2.I.i Six-Membered Rings	94
	2.I.ii Five-, Seven-, and Eight-Membered Rings	98
	2.I.iii Other Systems Containing Aromatic Sextets	103
	2.J Alternant and Nonalternant Hydrocarbons	104
	2.K Aromatic Systems with Electron Numbers Other Than Six	106
	2.K.i Systems of Two Electrons	108
	2.K.ii Systems of Four Electrons: Antiaromaticity	109
	2.K.iii Systems of Eight Electrons	112
	2.K.iv Systems of Ten Electrons	113
	2.K.v Systems of More than Ten Electrons: 4n+2 Electrons	116
	2.K.vi Systems of More Than Ten Electrons: 4n Electrons	121
	2.L Other Aromatic Compounds	125
	2.M Hyperconjugation	128
	2.N Tautomerism	132
	2.N.i Keto–Enol Tautomerism	133
	2.N.ii Other Proton-Shift Tautomerism	136
	3 Bonding Weaker Than Covalent	141
	3.A Hydrogen Bonding	141
	3.B ??????–?????? Interactions	149
	3.C Addition Compounds	150
	3.C.i Electron Donor–Acceptor (EDA) Complexes	150
	3.C.ii Crown Ether Complexes and Cryptates	153
	3.C.iii Inclusion Compounds	158
	3.C.iv Cyclodextrins	161
	3.D Catenanes and Rotaxanes	163
	3.E Cucurbit[n]Uril-Based Gyroscane	167
	4 Stereochemistry and Conformation	169
	4.A Optical Activity and Chirality	169
	4.B Dependence of Rotation on Conditions of Measurement	171
	4.C What Kinds of Molecules Display Optical Activity?	172
	4.D The Fischer Projection	183
	4.E Absolute Configuration	184
	4.E.i The Cahn-Ingold-Prelog System	186
	4.E.ii Methods Of Determining Configuration	188
	4.F The Cause of Optical Activity	192
	4.G Molecules with more than One Stereogenic Center	193
	4.H Asymmetric Synthesis	197
	4.I Methods of Resolution	202
	4.J Optical Purity	209
	4.K Cis–Trans Isomerism	211
	4.K.i Cis–Trans Isomerism Resulting from Double Bonds	211
	4.K.ii Cis–Trans Isomerism of Monocyclic Compounds	215
	4.K.iii Cis–Trans Isomerism of Fused and Bridged Ring Systems	216
	4.L Out–In Isomerism	217
	4.M Enantiotopic and Diastereotopic Atoms, Groups, and Faces	219
	4.N Stereospecific and Stereoselective Syntheses	222
	4.O Conformational Analysis	223
	4.O.i Conformation in Open-Chain Systems	224
	4.O.ii Conformation in Six-Membered Rings	230
	4.O.iii Conformation in Six-Membered Rings Containing Heteroatoms	235
	4.O.iv Conformation in Other Rings	238
	4.P Molecular Mechanics	240
	4.Q Strain	242
	4.Q.i Strain in Small Rings	243
	4.Q.ii Strain in Other Rings	249
	4.Q.iii Unsaturated Rings	251
	4.Q.iv Strain Due to Unavoidable Crowding	254
	5 Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes	259
	5.A Carbocations	260
	5.A.i Nomenclature	260
	5.A.ii Stability and Structure of Carbocations	260
	5.A.iii The Generation And Fate Of Carbocations	270
	5.B Carbanions	273
	5.B.i Stability and Structure	273
	5.B.ii The Structure Of Organometallic Compounds	280
	5.B.iii The Generation And Fate Of Carbanions	285
	5.C Free Radicals	286
	5.C.i Stability and Structure	286
	5.C.ii The Generation and Fate of Free Radicals	297
	5.C.iii Radical Ions	301
	5.D Carbenes	302
	5.D.i Stability and Structure	302
	5.D.ii The Generation and Fate of Carbenes	305
	5.D.iii N-Heterocyclic Carbenes (NHCs)	310
	5.E Nitrenes	312
	6 Mechanisms and Methods of Determining Them	315
	6.A Types of Mechanism	315
	6.B Types of Reaction	316
	6.C Thermodynamic Requirements for Reaction	319
	6.D Kinetic Requirements for Reaction	320
	6.E The Baldwin Rules for Ring Closure	324
	6.F Kinetic and Thermodynamic Control	326
	6.G The Hammond Postulate	327
	6.H Microscopic Reversibility	327
	6.I Marcus Theory	328
	6.J Methods of Determining Mechanisms	329
	6.J.i Identification of Products	329
	6.J.ii Determination of the Presence of an Intermediate	330
	6.J.iii The Study of Catalysis	331
	6.J.iv Isotopic Labeling	332
	6.J.v Stereochemical Evidence	332
	6.J.vi Kinetic Evidence	333
	6.J.vii Isotope Effects	340
	6.K Catalyst Development	344
	7 Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry	349
	7.A Photochemistry	350
	7.A.i Excited States and the Ground State	350
	7.A.ii Singlet and Triplet States: “Forbidden” Transitions	352
	7.A.iii Types of Excitation	353
	7.A.iv Nomenclature and Properties of Excited States	354
	7.A.v Photolytic Cleavage	355
	7.A.vi The Fate of the Excited Molecule: Physical Processes	356
	7.A.vii The Fate of the Excited Molecule: Chemical Processes	361
	7.A.viii The Determination of Photochemical MechanismsFor a review, see Calvert, J.G.	366
	7.B Sonochemistry	367
	7.C Microwave Chemistry	370
	7.D Flow Chemistry	372
	7.E Mechanochemistry	374
	8 Acids and Bases	375
	8.A Brønsted Theory	375
	8.A.i Brønsted Acids	376
	8.A.ii Brønsted Bases	383
	8.B The Mechanism of Proton Transfer Reactions	386
	8.C Measurements of Solvent Acidity	388
	8.D Acid and Base Catalysis	391
	8.E Lewis Acids and Bases	393
	8.E.i Hard–Soft Acids–Bases	395
	8.F The Effects of Structure on the Strengths of Acids and Bases	397
	8.G The Effects of the Medium on Acid and Base Strength	406
	9 Effects of Structure and Medium on Reactivity	411
	9.A Resonance and Field Effects	411
	9.B Steric Effects	413
	9.C Quantitative Treatments of the Effect of Structure on Reactivity	416
	9.D Effect of Medium on Reactivity and Rate	426
	9.E High Pressure	426
	9.F Water and Other Nonorganic Solvents	427
	9.G Ionic Liquid Solvents	429
	9.H Solventless Reactions	431
	PART II INTRODUCTION	433
	II.A IUPAC Nomenclature for Transformations	434
	II.B IUPAC System for Symbolic Representation of Mechanisms	434
	Step 1, First Symbol	435
	Step 1, Second Symbol	435
	Step 1, Combined Symbols	435
	Step 2	436
	Overall	436
	II.C Organic Syntheses References	436
	10 Aliphatic Substitution, Nucleophilic and Organometallic	439
	10.A Mechanisms	440
	10.A.i The SN2 Mechanism	440
	10.A.ii The SN1 Mechanism	446
	10.A.iii Ion Pairs in the SN1 Mechanism	450
	10.A.iv Mixed SN1 and SN2 Mechanisms	454
	10.B SET Mechanisms	456
	10.C The Neighboring-Group Mechanism	458
	10.C.i Neighboring-Group Participation by ?????? and ?????? Bonds: Nonclassical Carbocations	461
	10.D The SNi Mechanism	476
	10.E Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements	477
	10.F Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism	481
	10.G Reactivity	485
	10.G.i The Effect of Substrate Structure	485
	10.G.ii The Effect of the Attacking Nucleophile	493
	10.G.iii The Effect of the Leaving Group	500
	10.G.iv The Effect of the Reaction Medium	505
	10.G.v Phase-Transfer Catalysis	510
	10.G.vi Influencing Reactivity by External Means	513
	10.G.vii Ambident (Bidentant) Nucleophiles: Regioselectivity	514
	10.G.viii Ambident Substrates	517
	10.H Reactions	519
	10.H.i Oxygen Nucleophiles	519
	10.H.ii Sulfur Nucleophiles	542
	10.H.iii Nitrogen Nucleophiles	548
	10.H.iv Halogen Nucleophiles	570
	10.H.v Carbon Nucleophiles	581
	11 Aromatic Substitution, Electrophilic	643
	11.A Mechanisms	643
	11.A.i The Arenium Ion Mechanism	644
	11.A.ii The SE1 Mechanism	649
	11.B Orientation and Reactivity	650
	11.B.i Orientation and Reactivity in Monosubstituted Benzene Rings	650
	11.B.ii The Ortho/Para Ratio	654
	11.B.iii Ipso Attack	656
	11.B.iv Orientation in Benzene Rings With More Than One Substituent	657
	11.B.v Orientation in Other Ring Systems	658
	11.C Quantitative Treatments of Reactivity in the Substrate	660
	11.D A Quantitative Treatment of Reactivity of the Electrophile	662
	11.E The Effect of the Leaving Group	664
	11.F Reactions	665
	11.F.i Hydrogen as the Leaving Group in Simple Substitution Reactions	665
	11.F.ii Hydrogen As The Leaving Group In Rearrangement Reactions	711
	11.F.iii Other Leaving Groups	716
	12 Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic	723
	12.A Mechanisms	723
	12.A.i Bimolecular Mechanisms. SE2 and SEi	724
	12.A.ii The SE1 Mechanism	727
	12.A.iii Electrophilic Substitution Accompanied by Double-Bond Shifts	730
	12.A.iv Other Mechanisms	731
	12.B Reactivity	731
	12.C Reactions	733
	12.C.i Hydrogen as Leaving Group	733
	12.C.ii Metals as Leaving Groups	769
	12.C.iii Halogen as Leaving Group	782
	12.C.iv Carbon Leaving Groups	787
	12.C.v Electrophilic Substitution At Nitrogen	796
	13 Aromatic Substitution: Nucleophilic and Organometallic	803
	13.A Mechanisms	804
	13.A.i The SNAr Mechanism	804
	13.A.ii The SN1 Mechanism	807
	13.A.iii The Benzyne Mechanism	808
	13.A.iv The SRN1 Mechanism	810
	13.A.v Other Mechanisms	812
	13.B Reactivity	812
	13.B.i The Effect of Substrate Structure	812
	13.B.ii The Effect of the Leaving Group	814
	13.B.iii The Effect of the Attacking Nucleophile	815
	13.C Reactions	815
	13.C.i All Leaving Groups Except Hydrogen And N2+	815
	13.C.ii Hydrogen as Leaving Group	859
	13.C.iii Nitrogen as Leaving Group	860
	13.C.iv Rearrangements	870
	14 Radical Reactions	875
	14.A Mechanisms	875
	14.A.i Radical Mechanisms in General	875
	14.A.ii Free-Radical Substitution Mechanisms	880
	14.A.iii Mechanisms at an Aromatic Substrate	881
	14.A.iv Neighboring-Group Assistance in Free-Radical Reactions	883
	14.B Reactivity	884
	14.B.i Reactivity for Aliphatic Substrates	884
	14.B.ii Reactivity at a Bridgehead	889
	14.B.iii Reactivity in Aromatic Substrates	890
	14.B.iv Reactivity in the Attacking Radical	891
	14.B.v The Effect of Solvent on Reactivity	892
	14.C Reactions	892
	14.C.i Hydrogen as Leaving Group	892
	14.C.ii Metals as Leaving Groups	916
	14.C.iii Halogen as Leaving Group	919
	14.C.iv Sulfur as Leaving Group	919
	14.C.v Carbon as Leaving Group	921
	15 Addition to Carbon–Carbon Multiple Bonds	927
	15.A Mechanisms	928
	15.A.i Electrophilic Addition	928
	15.A.ii Nucleophilic Addition	931
	15.A.iii Free-Radical Addition	932
	15.A.iv Cyclic Mechanisms	934
	15.A.v Addition to Conjugated Systems	934
	15.B Orientation and Reactivity	935
	15.B.i Reactivity	935
	15.B.ii Orientation	938
	15.B.iii Stereochemical Orientation	940
	15.B.iv Addition to Cyclopropane Rings	942
	15.C Reactions	944
	15.C.i Isomerization of Double and Triple Bonds	944
	15.C.ii Reactions in Which Hydrogen Adds to One Side	946
	15.C.iii Reactions in Which Hydrogen Adds to Neither Side	1028
	15.C.iv Cycloaddition Reactions	1063
	16 Addition to Carbon–Heteroatom Multiple Bonds	1123
	16.A Mechanism and Reactivity	1123
	16.A.i Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism	1125
	16.B Reactions	1130
	16.B.i Reactions in Which Hydrogen or a Metallic Ion Adds to the Heteroatom	1131
	16.B.ii Acyl Substitution Reactions	1254
	16.B.iii Reactions in Which Carbon Adds to the Heteroatom	1293
	16.B.iv Addition to Isocyanides	1300
	16.B.v Nucleophilic Substitution at a Sulfonyl Sulfur Atom	1302
	17 Elimination Reactions	1309
	17.A Mechanisms and Orientation	1309
	17.A.i The E2 Mechanism	1310
	17.A.ii The E1 Mechanism	1316
	17.A.iii The E1cB Mechanism	1317
	17.A.iv The E1-E2-E1cB Spectrum	1322
	17.A.v The E2C Mechanism	1323
	17.B Regiochemistry of the Double Bond	1324
	17.C Stereochemistry of the Double Bond	1326
	17.D Reactivity	1327
	17.D.i Effect of Substrate Structure	1327
	17.D.ii Effect of the Attacking Base	1329
	17.D.iii Effect of the Leaving Group	1330
	17.D.iv Effect of the Medium	1330
	17.E Mechanisms and Orientation in Pyrolytic Eliminations	1331
	17.E.i Mechanisms	1331
	17.E.ii Orientation in Pyrolytic Eliminations	1334
	17.E.iii 1,4 Conjugate Eliminations	1334
	17.F Reactions	1335
	17.F.i Reactions in Which C=C and C?C Bonds Are Formed	1335
	17.F.ii Fragmentations	1357
	17.F.iii Reactions in Which C?N or C=N Bonds Are Formed	1361
	17.F.iv Reactions in Which C=O Bonds Are Formed	1364
	17.F.v Reactions in Which N=N Bonds Are Formed	1365
	17.F.vi Extrusion Reactions	1365
	18 Rearrangements	1371
	18.A Mechanisms	1372
	18.A.i Nucleophilic Rearrangements	1372
	18.A.ii The Actual Nature of the Migration	1373
	18.A.iii Migratory Aptitudes	1376
	18.A.iv Memory Effects	1379
	18.B Longer Nucleophilic Rearrangements	1380
	18.C Free-Radical Rearrangements	1381
	18.D Carbene Rearrangements	1385
	18.E Electrophilic Rearrangements	1385
	18.F Reactions	1386
	18.F.i 1,2-Rearrangements	1386
	18.F.ii Non 1,2-Rearrangements	1425
	19 Oxidations and Reductions	1475
	19.A Mechanisms	1476
	19.B Reactions	1478
	19.B.i Oxidations	1478
	19.B.ii Reductions	1546
	Appendix A The Literature of Organic Chemistry	1643
	A Primary Sources	1644
	A.i Journals	1644
	A.ii Patents	1645
	B Secondary Sources	1649
	B.i Listings of Titles	1649
	B.ii Abstracts	1650
	B.iii Beilstein	1653
	B.iv Tables of Information	1655
	C Reviews	1658
	C.i Annual Reviews	1659
	C.ii Awareness Services	1660
	C.iii General Treatises	1661
	C.iv Monographs and Treatises on Specific Areas	1663
	C.v Textbooks	1663
	C.vi Other Books	1664
	D Literature Searching	1666
	D.i Literature Searching Using Printed Materials	1666
	D.ii Literature Searching Online	1668
	D.iii Sci-Finder – the CAS database	1669
	D.iv Science Citation Index	1671
	D.v How to Locate Journal Articles	1675
	D.vi Reaxys®	1676
	Appendix B Classification of Reactions by Type of Compounds Synthesized	1681
	Author Index	1705
	Subject Index	1953
	EULA	2141