Strategies and solutions to advanced organic reaction mechanisms : a new perspective on McKillop's problems

__Strategies and Solutions to Advanced Organic Reaction Mechanisms: A New Perspective on McKillop's Problems__ builds upon Alexander (Sandy) McKillop’s popular text, __Solutions to McKillop’s Advanced Problems in Organic Reaction Mechanisms__, providing a unified methodological approach to dealing with problems of organic reaction mechanism. This unique book outlines the logic, experimental insight and problem-solving strategy approaches available when dealing with problems of organic reaction mechanism. These valuable methods emphasize a structured and widely applicable approach relevant for both students and experts in the field. By using the methods described, advanced students and researchers alike will be able to tackle problems in organic reaction mechanism, from the simple and straight forward to the advanced. * Provides strategic methods for solving advanced mechanistic problems and applies those techniques to the 300 original problems in the first publication * Replaces reliance on memorization with the understanding brought by pattern recognition to new problems * Supplements worked examples with synthesis strategy, green metrics analysis and novel research, where available, to help advanced students and researchers in choosing their next research project Front Matter Copyright Dedication Preface The Purpose of Writing This Book What This Book Offers Organization of Book and Layout of Solutions Acknowledgments References The Logic of Organic Reaction Mechanisms What is an Organic Chemical Reaction? The Balanced Chemical Equation What Is Contained in a Reaction Scheme? Principle of Conservation of Structural Aspect Curly Arrow Notation Baeyer-Villiger Oxidation Mechanism Table of Recommended Textbooks on Physical Organic Chemistry Base Strength and pKA Autoxidation References Evidence for Organic Reaction Mechanisms What Is Physical Organic Chemistry? Experimental Physical Organic Chemistry Applying Experimental Techniques-Baeyer-Villiger Oxidation Revisited References Problem Solving Organic Reaction Mechanisms Theoretical Problem-Solving Strategy Experimental Problem-Solving Strategy Case Study: Rearrangement of Cinenic Acid to Geronic Acid Current State of Pedagogy and Academic and Future Directions References Solutions 1 - 50 A Tandem Route to 1,2,3,4-Tetrasubstituted Naphthalenes Solution: 1 to 2 Solution: 2 to 3 Solution: D to 4 Balanced chemical equations Key Steps Explained Additional Resources References Hydroazulenes by Radical Cyclization Solution Balanced chemical equation Key Steps Explained Additional Resources References Cinnolines to Indoles Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Rearrangement During NMR Studies Solution Key Steps Explained Additional Resources References Synthesis of Trifluoromethyl Heterocycles Solution: 1 to 2 Solution: 2 to 3 Solution: 3 to 4 Balanced chemical equations Key Steps Explained Additional Resources References 3-Substituted Chromones From Pyranobenzopyrans Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Acid-Catalyzed Rearrangements of 1-Arylindoles Solution: 1 to 2 Balanced Chemical Equation Key Steps Explained Additional Resources References An Unusual Deprotection of an Aryl Ester Solution: 2 to 3 Balanced Chemical Equation Key Steps Explained Additional Resources References 3,1-Benzoxathiin Formation Solution: Mechanism 1 Solution: Mechanism 2 Key Steps Explained Additional Resources References Arylacetone Synthesis by Carroll-Type Rearrangement Solution: 1 and 2 to 3 Solution: 3 to 4 Key Steps Explained Additional Resources References Attempted Knoevenagel Reaction Gives Mannich-Type Products Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: 3 to 2 Balanced Chemical Equation: 3 to 2 Key Steps Explained Additional Resources References Pyridinium Salt Rearrangements Solution: 1 to 2 Solution: 3 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References A Pyridazine From a Thiophene Dioxide Solution: 1 and 2 to 3 Solution: 3 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Biomimetic Synthesis of Litebamine Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: 4 to 5 Solution: 5 to 6 Balanced Chemical Equation: 5 to 6 Key Steps Explained Additional Resources References Acid-Catalyzed Degradation of N-Nitroso-2,3-didehydromorpholine Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A New Route to 4-Amino-3-arylcinnolines Solution: 2 to 3 (Path a) Solution: 2 to 3 (Path b) Balanced Chemical Equation Key Steps Explained Additional Resources References Base-Induced Cyclizations of o-Ethynylaryl-Substituted Benzyl Alcohols Solution: 1 to 2 Solution: 3 to 5 Key Steps Explained Additional Resources References Trifluoromethylpyrroles From Trifluoromethyloxazolones Solution Balanced Chemical Equation Key Steps Explained Additional Resources References The Hooker Oxidation Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Synthesis of 1,3-Disubstituted Pyrroles Solution: 3 to 4 Balanced Chemical Equation Key Steps Explained Additional Resources References Grob Fragmentation of a 1-Azaadamantane Solution: 1 to 2 Balanced Chemical Equation Solution: 2 to 3 Balanced Chemical Equation Key Steps Explained Additional Resources References Selective Substitution of 3-Methoxypyrazine N-Oxide Solution: 1, 2, and 3 to 4 (When ZnBr2 Present) Balanced Chemical Equation Key Steps Explained Additional Resources References Reactions of Ethacrylate Esters With NO2BF4 Solution: 1 to 2 Solution: A to 3 Solution: 4 to 5 Balanced Chemical Equation: 4 to 5 Solution: C to 6 Balanced Chemical Equation: 4 to 6 Key Steps Explained Additional Resources References A Furan Synthesis Solution: 1 to 2 Solution: 2 to 3 (Authors Mechanism) Balanced Chemical Equations Key Steps Explained Additional Resources References Dimerization of Vinca Alkaloids Solution Key Steps Explained Additional Resources References Nitration of a Quinoline Derivative Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Synthesis of Binaphthyldiquinones Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Heterocyclic Fun With DMAD Solution: Mechanism 1 Solution: Mechanism 2 Balanced Chemical Equation Key Steps Explained Additional Resources References Unexpected Formation of a 1,5-Benzodiazonine Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Thiopyran to Thiophene Transformation Solution: 1 to 2 Solution: 3 to 4 (Path a: F to 4) Solution: 3 to 4 (Path b: F to 4) Balanced Chemical Equations Key Steps Explained Additional Resources References Skeletal Rearrangements of a Diterpene Solution: 1 to 2 Solution: B to 4 Solution: 4 to 3 Solution: 3 to 5 Balanced Chemical Equations Key Steps Explained Additional Resources References Reissert Reactions of Quinoxaline N-Oxides Solution: 1 to 2 Solution: 1 to 3 Solution: 4 to 5 Balanced Chemical Equations Key Steps Explained Additional Resources References Unexpected Results in Directed Metalation Solution: 3 to 4/5 Key Steps Explained Additional Resources References 1,4-Dioxene in Synthesis Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Collins Oxidation of Phenylethanols Solution: 1 to 2 Solution: 4 to 5 Balanced Chemical Equations Key Steps Explained Additional Resources References Allene Sulfoxide Rearrangement Solution: 2 to 3 Solution: 3 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References A Failed ``Pinacol-Type ́ ́ Rearrangement Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Allylation of 1,4-Benzoquinones Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Benzopyrene Synthesis-By Accident Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Rearrangement of Ketene Acetals Solution: 2E to 3 Solution: 2Z to 3 Balanced Chemical Equation Key Steps Explained Additional Resources References Nucleophilic Additions to a Heterocyclic o-Quinone Solution: 1 to 2 Solution: 1 to 3 Key Steps Explained Additional Resources References How Mitomycin C Can Crosslink DNA Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Two Carbon Ring Expansions of Cycloalkanones Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: 3 to 4 Balanced Chemical Equation: 3 to 4 Solution: 3 to 5 Balanced Chemical Equation: 3 to 5 Key Steps Explained Additional Resources References Fulgides: Synthesis and Photochromism Solution: 1 and 2 to 3 (Stobbe Condensation) Balanced Chemical Equation: 1 and 2 to 3 Solution: 3 to 4 (Lactone Opening Esterification) Balanced Chemical Equation: 3 to 4 Solution: 4 to 5 (Stobbe Condensation) Balanced Chemical Equation: 4 to 5 Solution: 5 to 6 (Saponification of Diester to Diacid) Balanced Chemical Equation: 5 to 6 Solution: 6 to 7 Balanced Chemical Equation: 6 to 7 Solution: 7 to 8 (Base-Assisted Ring Opening Alkylation) Balanced Chemical Equation: 7 to 8 Solution: 8 to 9 (Acetyl Chloride-Assisted Cyclization) Balanced Chemical Equation: 8 to 9 Solution: 9 to 10 (Photochromism Mechanism) Key Steps Explained Additional Resources References Benzodiazepines From (R)-(+)-Pulegone Solution Key Steps Explained Additional Resources References A Furan to Pyran Ring Expansion Solution: 1 to 2 (Mechanism 1: Consistent With Deuterium Labeling Study) Solution: 1 to 2 (Mechanism 2: Inconsistent With Deuterium Labeling Study) Key Steps Explained References A Structure and Mechanism Correction Solution: 1 and 2 to 3 (Claimed Reaction) Solution: 3 to 4 (Claimed Reaction) Solution: 1 and 2 to 5 (Actual Reaction) Solution: 5 to 4 (Actual Reaction) Balanced Chemical Equations Key Steps Explained Additional Resources References Propargylbenzotriazoles to Five-membered Heterocycles Solution: 1 and 2 to 3 Balanced Chemical Equation: 1 and 2 to 3 Solution: 3 to 4 Balanced Chemical Equation: 3 to 4 Key Steps Explained Additional Resources References From Carvone to an Isoxazoloazepine Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Isoxazoles From Cyclopropanes Solution: 1 to 2 Balanced Chemical Equation Key Steps Explained Additional Resources References Solutions 51 - 100 A Radical Cascade From a Ketene Dithioacetal Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Synthesis of 3-Alkyl-1-naphthols Solution: 2 to 3 Solution: 4 to 5 Solution: 6 to 7 Key Steps Explained Additional Resources References An Entry to Indole Alkaloids of Unusual Structural Type Solution: 1 to 2 Solution: 2 to 3 Solution: 3 to 5 and 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Cyclization as a Key Step to Hirsutene Solution Key Steps Explained Additional Resources References A 1,3-Cyclopentanedione to 1,4-Cyclohexanedione Transformation Solution: Originally Proposed Mechanism for 1 to 2 Solution: Revised Mechanism for 1 to 2 Part 1: 1 to 3 Solution: Revised Mechanism for 1 to 2 Part 2: 3 to 2 Key Steps Explained Additional Resources References Conversion of o-Hydroxyaryl Ketones Into 1,2-Diacylbenzenes Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Mechanisms of Bimane Formation Solution: 1 to syn-2 Solution: A and B to anti-2 Balanced Chemical Equation: 1 to syn-2/anti-2 Solution: 3 to syn-4 Balanced Chemical Equation: 3 to syn-4 Key Steps Explained Additional Resources References A Carbohydrate to Cyclopentanol Conversion Solution Balanced Chemical Equation Key Steps Explained Balanced Chemical Equation: Scheme 2 Balanced Chemical Equation: Scheme 3 Balanced Chemical Equation: Scheme 4 Additional Resources References Pyridazines From 1,2,4-Triazines Solution: 1 to 2 Using 15N Label on Phenylacetonitrile Solution: 2 to 3 Using 15N Label on Phenylacetonitrile Balanced Chemical Equations Key Steps Explained Additional Resources References Natural Product Degradation During Extraction and/or Chromatography Solution: Authors Proposal (Ionic Mechanism) Solution: Alternative Proposal (Radical Mechanism) Balanced Chemical Equation Key Steps Explained Additional Resources References Simple Access to Oxaadamantanes Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: I to 3 Balanced Chemical Equation: 1 to 3 Solution: D to 4 Balanced Chemical Equation: 1 to 4 Key Steps Explained Additional Resources References A Pyrimidine Rearrangement Solution Balanced Chemical Equation Key Steps Explained Additional Resources References 1,4-Thiazin-3-ones From 1,4-Oxathiins Solution Balanced Chemical Equation Key Steps Explained Additional Resources References An Unusual Route to 3-Acylfurans Solution: 1 to 2 Solution: 2 to 3 Balanced Chemical Equations Key Steps Explained Additional Resources References Reaction of PQQ With l-Tryptophan Solution Additional Resources References An Unexpected Result From an Attempted Double Bischler-Napieralski Reaction Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Bis-Indole Alkaloid Formation Solution: 1 to 2 Solution: 3 to 4 and 5 Solution: 6 to 7 and 8 Balanced Chemical Equations Key Steps Explained Additional Resources References Azaphenalene Alkaloid Synthesis: A Key Step Solution: Path A Solution: Path B (C to 2 Alternative) Balanced Chemical Equation Key Steps Explained Additional Resources References A Primary Nitroalkane to Carboxylic Acid Transformation Solution: 1 to 2 Solution: 3 to 2 Balanced Chemical Equations Key Steps Explained Additional Resources References α-Diazoketones With Rhodium(II) Acetate Solution: 1 to 2 Solution: E to 3 Solution: C to J and 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Pyrrolo[1,2-a]benzimidazole Synthesis by Ortho Nitro Interaction Solution: 1 to 2 Solution: H to 3 Solution: H to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Horner-Wittig Reaction on a Bifuranylidenedione Solution: 1 and 2 to 3 Solution: 3 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Lactone Ammonolysis Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Intramolecular Schmidt Reaction Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Indolizidones by Intermolecular Photochemical Reaction Solution: 1 to E Solution: E to G Solution: G to 3 (Author Mechanism) Solution: G to 3 (Alternative Proposal) Balanced Chemical Equations Key Steps Explained Additional Resources References An Unexpected Product From Amine Oxidation Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Degradation of Pyripyropene A Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: 2 to 3 and 4 Balanced Chemical Equation: 2 to 3 and 4 Key Steps Explained Additional Resources References Benzofurans From Cyclobutenediones Solution: 1 and 2 to 3 Solution: 3 to 4 Solution: 4 to 5 Solution: 5 to 6 Balanced Chemical Equations Key Steps Explained Additional Resources References Acid-Catalyzed Condensation of Indole With Acetone Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Synthesis of 2-Formylpyrrolidines Solution: 1 to 2 Solution: 2 to 3 Balanced Chemical Equation: 2 to 3 Solution: 3 to 4 Key Steps Explained Additional Resources References An Abnormal Claisen Rearrangement Solution Key Steps Explained Additional Resources References Benzoxepinones From Phthalides Solution Balanced Chemical Equation Key Steps Explained Additional Resources References m-Terphenyls From Pyrones Solution: 1 to 2 Solution: B to 3 Balanced Chemical Equations Key Steps Explained Additional Resources References A Cascade Reaction Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Photochemical Ortho Rearrangements Solution: 1 to 3 Balanced Chemical Equations Key Steps Explained Additional Resources References From Bicycle to Pentacycle to Tricycle Solution: 1 and 2 to 3 Solution: 3 to 4 Balanced Chemical Equation Key Steps Explained Additional Resources References Lewis Acid-Catalyzed Cyclopropyl Ketone Rearrangement Solution Key Steps Explained Additional Resources References An Intramolecular Ring Closure Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Photochemical Rearrangement of Pyran-2-ones Solution: 1 to 2 Solution: F to H (Alternative Path) Key Steps Explained Additional Resources References A Paclitaxel Rearrangement Solution Balanced Chemical Equation Key Steps Explained Additional Resources References An Ionic Diels-Alder Reaction Solution Balanced Chemical Equation Key Steps Explained Additional Resources References The Eschenmoser Fragmentation Reaction Extended Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Modified Batcho-Leimgruber Synthesis Solution: 1 to 4 p-TsOH Acid Catalysis Key Steps Explained Additional Resources References A Pyrone to Pyran Conversion Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Conformationally Rigid 4-Oxoquinolines Solution Balanced Chemical Equation Key Steps Explained Additional Resources References An Efficient Chromene Synthesis Solution: 1 and 2 to 3 Solution: 3 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Flash Vacuum Pyrolysis of o-Xylylene Dimers Solution: 1 to 2 Solution: 3 to 4 Key Steps Explained Additional Resources References Synthesis of a Neocarzinostatin Building Block Solution Key Steps Explained Additional Resources References Oxazole Esters From α-Amino Acids Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Unexpected Formation of a Phenazine Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Solutions 101 - 150 Conversion of Primary Amides Into Nitriles Solution Balanced Chemical Equation Key Steps Explained Additional Resources References An Efficient Benzo[b]fluorene Synthesis Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Facile Synthesis of Tetracyclic Pyrroloquinazolines Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Ethyl 2-Chloronicotinate From Acyclic Precursors Solution: 1, 2, and 3 to 4 Solution: 4 to 5 Balanced Chemical Equation: 1, 2, and 3 to 4 Balanced Chemical Equation: 4 to 5 Key Steps Explained Additional Resources References A 2-Arylpropanoic Acid Synthesis Solution: 1 to 2 Solution: 2 to 3 Solution: 3 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Synthesis of Isoquinolin-4-ones Solution: 1 to 2 Solution: 1 to 3 Key Steps Explained Additional Resources References Naphthopyrandione From 1,4-Naphthoquinone Solution: 1a to 3 Solution: 1b to 4 Balanced Chemical Equations Key Steps Explained Reference A Photochromic Product for Sunglasses Solution: 1 to 2 Solution: 2 to 3 Balanced Chemical Equations Key Steps Explained Additional Resources References A Quick Entry to the Aklavinone Ring System Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A ``Stable Enol ́ ́ That Doesnt Exist Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Conversion of an Indole-Based Bicyclo[5.3.1]undecane Into a Bicyclo[5.4.0]undecane Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Classical Mannich Approach to Isoquinoline Alkaloids Leads to an Unexpected Product Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Reaction of Benzothiazole With DMAD Solution Key Steps Explained Additional Resources References Inhibition of the l-DOPA to l-Dopaquinone Oxidation Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A One-Pot Synthesis of 1,3,6,8-Tetramethyl-2,7-naphthyridine Solution: Formation of 1 Part 1 (A to H) Solution: Formation of 1 Part 2 (H to 1 Path A) Solution: Formation of 1 Part 3 (H to 1 Path B) Solution: Formation of 1 Part 4 (ALTERNATE ROUTE: B to O1) Solution: Formation of 1 Part 5 (ALTERNATE ROUTE: S to H) Solution: Formation of 2 Balanced Chemical Equations Key Steps Explained References Unexpected Course of a Mannich Reaction in Alkaloid Synthesis Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Synthesis of Thioindigo Solution Balanced Chemical Equation Key Steps Explained Additional Resources References An Unexpected Reaction During Studies of Amine Oxide Rearrangements Solution: 1 to 3 (Expected Product) Solution: 1 to 2 (Observed Product) Balanced Chemical Equation Key Steps Explained Additional Resources References An Unusual Phosphite-Induced Deoxygenation of a Nitronaphthalene Solution: 1 to 2 Authors Mechanism Solution: 1 to 2 Alternative Mechanism Solution: 3 to 2 Authors Mechanism Solution: 3 to 2 Alternative Mechanism Balanced Chemical Equation Key Steps Explained Additional Resources References A Benzimidazole to Pyrroloquinoxaline Transformation Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Acid-Catalyzed Benzophenone Isomerization Solution: Hayashi Mechanism1 Solution: Sandin Mechanism2 Solution: Wang Mechanism3 Key Steps Explained Additional Resources References 2-Oxabicyclo[1.1.0]butanone Is Not Easily Accessible Solution: Authors Mechanism Solution: Alternative Mechanism Balanced Chemical Equation Key Steps Explained Additional Resources References A Simple Synthesis of the Indole Alkaloid Yuehchukene Solution Key Steps Explained Additional Resources References Isoquinoline Rearrangement Solution Key Steps Explained Additional Resources References Multiple Sigmatropic Rearrangements Solution: 1 to 2 in PhCl Solution: 1 to 2 and 3 in PhCl and AIBN Solution: 1 to 3 in pTsOH Key Steps Explained Additional Resources References A Vilsmeier-Induced Annulation to Benzene Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Isopropylidene to 2-Alkyne Conversion Solution: Corey2 Mechanism Solution: Zard4 Mechanism Balanced Chemical Equations Key Steps Explained Additional Resources References A Tryptamine to Pentacyclic Indoline Transformation Solution: 1 to 2 Catalyst Regeneration Balanced Chemical Equation: 1 to 2 Solution: 1 to 3 Balanced Chemical Equation: 1 to 3 Key Steps Explained Additional Resources References Ring Contractions of a Dibenzothiepinone Solution: 1 to 2 Solution: 1 to 3 Solution: 1 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References Steroid Fragmentation With DDQ Solution: 1 to 2 Solution: 1 to 3 Solution: 1 to 4 Balanced Chemical Equations Key Steps Explained Additional Resources References A Base-Induced Vinylcyclopropane Rearrangement Solution Balanced Chemical Equation Key Steps Explained Additional Resources References 4-Demethoxydaunomycin: The Desired Result, but Not According to Plan Solution: 1 to 3 Solution: 3 to 4 Solution: 4 to 5 Solution: 5 to 2 Key Steps Explained Additional Resources References Three Isomeric Hexadienols Give the Same Bicyclic Lactone Solution: 1 to 4 Solution: 2 to 4 Solution: 3 to 4 Key Steps Explained Additional Resources References Degradation of Antibiotic X-537A Solution: 2 to 3 and A Solution: A to 5 Balanced Chemical Equation: 2 to 3 and 5 Solution: 2 to 4 Solution: D to 6 Balanced Chemical Equation: 2 to 3 and 6 Key Steps Explained Additional Resources References Steroid Rearrangements: Appearances Can Be Deceptive Solution Additional Resources References Synthesis of Eburna and Aspidosperma Alkaloids Solution: 2 to 3a and 3b Balanced Chemical Equation: 2 to 3a and 3b Solution: 2 to 4 and 5 Balanced Chemical Equations: 2 to 4 and 5 Key Steps Explained Additional Resources References Synthesis of Highly Hindered Cyclic Amines Solution: 1 to 2 Solution: 1 to 3 Balanced Chemical Equations: 1 to 2 and 3 Solution: 4 to 5 and 6 Balanced Chemical Equations: 4 to 5 and 6 Key Steps Explained Additional Resources References A 1,2-Dihydrobenzocyclobutane to Isochroman-3-one Conversion Solution Key Steps Explained Additional Resources References An Unexpectedly Facile Decarboxylation Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Regiospecific Synthesis of a 1,2-Dihydronaphthalene Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Degradation of Terramycin Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Synthesis of Bi-indane-l,3-dione Solution: 1 and 2 to 3 Solution: 3 to 4 Solution: 4 to 5 Solution: 5 to 6 Key Steps Explained Additional Resources References A Coumarin to Cyclopentenone Transformation Solution Balanced Chemical Equation Key Steps Explained Additional Resources References ``Synthetic Heroin ́ ́ and Parkinsonism Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Rearrangement of 6-Hydroxyprotopine to Dihydrosanguinarine Solution Key Steps Explained Additional Resources References Biotin Synthesis: Sulfur Preempts a Beckmann Rearrangement Solution Key Steps Explained Additional Resources References A 1,4-Dithiin to Thiophene Rearrangement Solution: 1 to 2 Solution: 1 to 3 Balanced Chemical Equation: 1 to 3 Key Steps Explained Additional Resources References An Intramolecular Wittig Reaction Solution: 1 to 2 Solution: 1 to 3 Key Steps Explained Additional Resources References Amination of a Cephalosporin Solution: 1 to 2 Solution: 2 to 3 Key Steps Explained Additional Resources References A Uracil to 1,2,3-Triazole Conversion Solution: Authors Mechanism Solution: Alternative Mechanism Balanced Chemical Equation Key Steps Explained Additional Resources References Solutions 151 - 200 Schumm Devinylation of Vinyl Porphyrins Solution: Mechanism 1A Solution: Mechanism 1B Solution: Mechanism 2A Solution: Mechanism 2B Solution: Mechanism 3 Solution: Mechanism 4 Key Steps Explained Additional Resources References A Uracil to Substituted Benzene Transformation Solution: 1 to 2 Solution: 1 to 3 Key Steps Explained Additional Resources References γ-Lactones From Vinyl Sulfoxides Solution Key Steps Explained Additional Resources References Tetrahydrothieno[2,3-c]- and -[3,2-c]pyridine Synthesis Solution: 1 to 2 (Weakly Acidic Medium) Solution: 1 to 2 and 3 (Strongly Acidic Medium) Key Steps Explained Additional Resources References Oxothiolan Oxathian Oxothiolan Oxathian Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: 2 to 3 Balanced Chemical Equation: 2 to 3 Solution: 3 to 4 Balanced Chemical Equation: 3 to 4 Key Steps Explained Additional Resources References A Thiazolopyrimidine to Pyrrolopyrimidine Transformation Solution: 1 and 2 to 3 Balanced Chemical Equation: 1 and 2 to 3 Solution: 3 to 6 to 5 Balanced Chemical Equation: 3 to 6 to 5 Solution: 5 to 4 Key Steps Explained Additional Resources References Oxidation of 1,5-Diacetoxynaphthalene With NBS Solution: 1 to 3 to 2 Balanced Chemical Equation: 1 to 3 Balanced Chemical Equation: 3 to 2 Balanced Chemical Equation: 4 to 2 Key Steps Explained Additional Resources References Badly Chosen Reaction Conditions? Solution Balanced Chemical Equation Key Steps Explained Additional Resources References One Step Synthesis of a Highly Symmetrical Hexacyclic System From a Simple Naphthol Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Method for Aryloxylation of p-Cresol Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: 2 to 3 Solution: 2 to 3 Alternative Balanced Chemical Equation: 2 to 3 Solution: 3 to 4 Balanced Chemical Equation: 3 to 4 Solution: 3 to 5 Balanced Chemical Equation: 3 to 5 Key Steps Explained Additional Resources References Nitriles From N-Chlorosulfonylamides Solution: Nitrile Formation Via Triethylamine Solution: Nitrile Formation Via Dimethylformamide (DMF) Key Steps Explained Additional Resources References Synthesis of Perylenequinone Solution Balanced Chemical Equation Balanced Chemical Redox Equation Key Steps Explained Additional Resources References A Route to 2-Vinylindoles Solution Key Steps Explained Additional Resources References Brain Cancer: The Mechanism of Action of Temozolomide Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Attempted Nef-Type Reaction Leads to 3-Arylpyridine Synthesis Solution: Part 1-Reduction Solution: Part 2-Rearrangement Balanced Chemical Equation Key Steps Explained Additional Resources References The ArCOMe ArCCH Transformation Solution: 1 to 2 Balanced Chemical Equation: 1 to 2 Solution: 2 to 3 Balanced Chemical Equation: 2 to 3 Key Steps Explained Additional Resources References β-Amino Nitriles From Azetidones Solution Key Steps Explained Additional Resources References A New Route to 1,3-Disubstituted Naphthalenes Solution Balanced Chemical Equation Key Steps Explained Additional Resources References An Efficient Annulation Route to 6-Substituted Indoles Solution Balanced Chemical Equation Key Steps Explained Additional Resources References Failure of a Rearrangement: From a Useful Compound to a Useless Product Solution Key Steps Explained Additional Resources References Synthesis of Trisubstituted Isoxazoles Solution: 1 to 2 and 2 to 3 Balanced Chemical Equation Key Steps Explained Additional Resources References 2,3-Dihydrobenzofurans From 1,4-Benzoquinones Solution: 1 and 2 to 3 and 3 to 4 Solution: 5 and 6 to 7 Solution: 7 to 8 Balanced Chemical Equation Key Steps Explained Additional Resources References Easy Construction of a Tricyclic Indole Related to the Mitomycins Solution: 1 to 2 Solution: 2 to 3 Key Steps Explained Additional Resources References Cycloaddition to a Benzothiopyrylium Salt Solution: 3 to 4 Solution: 3 to 5 Key Steps Explained Additional Resources References Benzotriazole From 1,2,4-Benzotriazine N-Oxides Solution: 1 to 3 Solution: 2 to 3 Key Steps Explained Additional Resources References A Furan Furan Transformation Solution Key Steps Explained Additional Resources References Ring Expansion of Both Rings of Penicillin Sulfoxides Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Retro-Pictet-Spengler Reaction Solution: Epimerization Mechanism 1 (C1N2 Bond Scission) Solution: Epimerization Mechanism 2 (Olefin Protonation) Solution: Epimerization Mechanism 3 (Iminium Ion Formation) Solution: Degradation Mechanism 1 (Retro-Pictet-Spengler) Path A Solution: Degradation Mechanism 1 (Retro-Pictet-Spengler) Path B Key Steps Explained Additional Resources References An Olefin to α-Hydroxy Ketone Transformation Solution Balanced Chemical Equation Key Steps Explained Additional Resources References A Benzofuran From a Cyclopropachromone Solution Balanced Chemical Equation Key Steps Explained A