McKillop A. (ed.) Tetrahedron Organic Chemistry. Volume 16. Advanced Problems in Organic Reaction Mechanisms

Pergamon, 1997. — 153 p. — ISBN: 978-0-08-043256-4Every student of organic chemistry is taught the subject on a mechanism basis, and almost all research in organic chemistry is mechanism based. During the last few years there have been a number of new books and revised editions of older books on the theory and principles of organic reaction mechanisms, but few contain problems on which the reader can test his or her skills and understanding of the subject. Major undergraduate textbooks do have sets of problems which are useful at the introductory level, but there are no recent specialist books of problems at a more advanced level.
This book is a collection of 300 problems which challenge the user to devise reasonable mechanistic interpretations for sets of experimental observations. Almost all of the problems are taken from the literature of the last twenty years. Each is a separate entity, although similar mechanistic themes occur in several quite different problems. Answers are not given, nor are references to the original literature. The user who fails to solve a particular problem and reaches an appropriate level of frustration should be able, relatively quickly, to locate the original literature from the information given in the problem.List Of Problems
A Tandem Route to 1,2,3,4-Tetrasubstimted Naphthalenes
Hydroazulenes by Radical Cyclisation
Cinnolines to Indoles
Rearrangement During NMR Studies
Synthesis of Trifluoromethyl Heterocycles
Substituted Chromones from Pyranobenzopyrans
Acid-Catalysed Rearrangments of 1-Arylindoles
An Unusual Deprotection of an Aryl Ester
3,1-Benzoxathiin Formation
Arylacetone Synthesis by Carroll-Type Rearrangement
Attempted Knoevenagel Reaction Gives Mannich-Type Products
Pyridinum Salt Rearrangements
A Pyridazine from a Thiophene Dioxide
Biomimetic Synthesis of Litebamine
Acid-Catalysed Degradation of N-Nitroso-2,3-didehydromorpholine
A New Route to 4-Amino-3-arylcinnolines
Base-Induced Cyclisations of o-Ethynylaryl-Substituted Benzyl Alcohols
Trifluoromethylpyrroles from Trifluoromethyloxazolones
The Hooker Oxidation
Synthesis of 1,3-Disubstituted Pyrroles
Grob Fragmentation of a 1-Azaadamantane
Selective Substitution of 3-Methoxypyrazine N-Oxide
Reactions of Ethacrylate Esters with NO2BF
A Furan Synthesis
Dimerisation of Vinca Alkaloids
Nitration of a Quinoline Derivative
Synthesis of Binaphthyldiquinones
Heterocyclic Fun with DMAD
Unexpected Formation of a 1,5-Benzodiazonine
A Thiopyran to Thiophene Transformation
Skeletal Rearrangements of a Diterpene
Reissert Reactions of Quinoxaline N-Oxides
Unexpected Results in Directed Metallation
1,4-Dioxene in Synthesis
Collins Oxidation of Phenylethanols
Allene Sulfoxide Rearrangement
A Failed "Pinacol-Type" Rearrangement
AUylation of 1,4-Benzoquinones
Benzopyrene Synthesis- By Accident
Rearrangement of Ketene Acetals
Nucleophilic Additions to a Heterocyclic o-Quinone
How Mitomycin C Can Crosslink DNA
Two Carbon Ring Expansions of Cycloalkanones
Fulgides: Synthesis and Photochromism
Benzodiazepines from (R)-(+)-Pulegone
A Furan to Pyran Ring Expansion
A Structure and Mechanism Correction
Propargylbenzotriazoles to Five-membered Heterocycles
From Carvone to an Isoxazoloazepine
Isoxazoles from Cyclopropanes
A Radical Cascade from a Ketene Dithioacetal
A Synthesis of 3-Alkyl-l-Naphthols
An Entry to Indole Alkaloids of Unusual Structural Type
Cyclisation as a Key Step to Hirsutene
A 1,3-Cyclopentanedione to 1,4-Cyclohexanedione Transformation
Conversion of o-Hydroxyaryl Ketones into 1,2-Diacylbenzenes
Mechanisms of Bimane Formation
A Carbohydrate to Cyclopentanol Conversion
Pyridazines from 1,2,4-Triazines
Natural Product Degradation During Extraction and/or Chromatography
Simple Access to Oxaadamantanes
A Pyrimidine Rearrangement
1,4-Thiazin-3-ones from 1,4-Oxathiins
An Unusual Route to 3-Acylfurans
Reaction of PQQ with L-Tryptophan
An Unexpected Result from an Attempted Double Bischler-Napierski
Reaction
Bis-indole Alkaloid Formation
Azaphenalene Alkaloid Synthesis : A Key Step
A Primary Nitroalkane to Carboxylic Acid Transformation
α-Diazo Ketones with Rhodium(U) Acetate
Pyrrolo[1,2-a]benzimidazole Synthesis by Ortho Nitro Interaction
Horner-Wittig Reaction on a Bifuranylidenedione
Lactone Ammonolysis
Intramolecular Schmidt Reaction
ndolizidones by Intermolecular Photochemical Reaction
An Unexpected Product from Amine Oxidation
Degradation of Pyripyropene A
Benzofurans from Cyclobutenediones
Acid-Catalysed Condensation of Indole with Acetone
A Synthesis of 2-Formylpyrrolidines
An Abnormal Claisen Rearrangement
Benzoxepinones from Phthalides
m-Terphenyls from Pyrones
A Cascade Reaction
Photochemical Ortho Rearrangements
From Bicycle to Pentacycle to Tricycle
Lewis Acid-Catalysed Cyclopropyl Ketone Rearrangement
An Intramolecular Ring Closure
Photochemical Rearrangement of Pyran-2-ones
A Paclitaxel Rearrangement
An Ionic Diels-Alder Reaction
The Eschenmoser Fragmentation Reaction Extended
A Modified Batcho-Leimgruber Synthesis
A Pyrone to Pyran Conversion
Conformationally Rigid 4-Oxoquinolines
An Efficient Chromene Synthesis
Flash Vacuum Pyrolysis of o-Xylylene Dimers
Synthesis of a Neocarzinostatin Building Block
Oxazole Esters from (x-Amino Acids
Unexpected Formation of a Phenazine
Conversion of Primary Amides into Nitriles
An Efficient Benzo[b]fluorene Synthesis
A Facile Synthesis of Tetracyclic Pyrroloquinazolines
Ethyl 2-Chloronicotinate from Acyclic Precursors
A 2-Arylpropanoic Acid Synthesis
Synthesis of Isoquinolin-4-ones
Naphthopyrandione from 1,4-Naphthoquinone
A Photochromic Product for Sunglasses
A Quick Entry to the Aklavinone Ring System
A "Stable Enor' that Doesn't Exist
Conversion of an Indole-Based Bicyclo[5.3.1]undecane into a Bicyclo[5.4.0]undecane
A Classical Mannich Approach to Isoquinoline Alkaloids Leads to an Unexpected Product
Reaction of Benzothiazole with DMAD
Inhibition of the L-DOPA to L-Dopaquinone Oxidation
A One-Pot Synthesis of 1,3,6,8-Tetramethyl-2,7-naphthyridine
Unexpected Course of a Mannich Reaction in Alkaloid Synthesis
Synthesis of Thioindigo
An Unexpected Reaction During Studies of Amine Oxide Rearrangements
An Unusual Phosphite-Induced Deoxygenation of a Nitronaphthalene
A Benzirnidazole to Pyrroloquinoxaline Transformation
Acid-Catalysed Benzophenone Isomerisation
Oxabicyclo[1.1.0]butanone is not Easily Accessible
A Simple Synthesis of the Indole Alkaloid Yuehchukene
Isoquinoline Rearrangement
Multiple Sigmatropic Rearrangements
A Vilsmeier-Induced Annulation to Benzene
Isopropylidene to 2-Alkyne Conversion
A Tryptamine to Pentacyclic Indole Transformation
Ring Contractions of a Dibenzothiepinone
Steroid Fragmentation with DDQ
A Base-Induced Vinylcyclopropane Rearrangement
Demethoxydaunomycin 9T he Desired Result, but not According to Plan
Three Isomeric Hexadienols Give the Same Bicyclic Lactone
Degradation of Antibiotic X-537A
Steroid Rearrangements 9A ppearances Can Be Deceptive
Synthesis of Eburna and Aspidosperma Alkaloids
Synthesis of Highly Hindered Cyclic Amines
A 1,2-Dihydrobenzocyclobutane to Isochroman-3-one Conversion
An Unexpectedly Facile Decarboxylation
Regiospecific Synthesis of a 1,2-Dihydronaphthalene
Degradation of Terramycin
Synthesis of Bi-indane- 1,3-dione
A Coumarin to Cyclopentenone Transformation
"Synthetic Heroin" and Parkinsonism
Rearrangement of 6-Hydroxyprotopine to Dihydrosanguinarine
Biotin Synthesis : Sulfur Preempts a Beckmann Rearrangement
A 1,4-Dithiin to Thiophene Rearrangement
An Intramolecular Wittig Reaction
Amination of a Cephalosporin
A Uracil to 1,2,3-Triazole Conversion
Schumm Devinylation of Vinyl Porphyrins
A Uracil to Substituted Benzene Transformation
γ-Lactones from Vinyl Sulfoxides
Tetrahydrothieno[2,3-c]- and -[3,2-c]pyridine Synthesis
Oxothiolan → Oxathian → Oxothiolan → Oxathian
A Thiazolopyrimidine to Pyrrolopyrimidine Transformation
Oxidation of 1,5-Diacetoxynaphthalene with NBS
Badly Chosen Reaction Conditions?
One Step Synthesis of a Highly Symmetrical Hexacyclic System from a Simple Naphthol
A Method for Aryloxylation of p-Cresol
Nitriles from N-Chlorosulfonylamides
Synthesis of Perylenequinone
A Route to 2-Vinylindoles
Brain Cancer: The Mechanism of Action of Temozolomide
Attempted Nef-Type Reaction Leads to 3-Arylpyridine Synthesis
The ArCOMe → ArC[triple bond]CH Transformation
J-Amino Nitriles from Azetidones
A New Route to 1,3-Disubstituted Naphthalenes
An Efficient Annulation Route to 6-Substituted Indoles
Failure of a Rearrangement : from a Useful Compound to a Useless Product
Synthesis of Trisubstituted Isoxazoles
1,3-Dihydrobenzofurans from 1,4-Benzoquinones
Easy Construction of a Tricyclic Indole Related to the Mitomycins
Cycloaddition to a Benzothiopyrylium Salt
Benzotriazole from 1,2,4-Benzotriazine N-Oxides
A Furan → Furan Transformation
Ring Expansion of Both Rings of Penicillin Sulfoxides
A Retro-Pictet-Spengler Reaction
An Olefin to α-Hydroxy Ketone Transformation
A Benzofuran from a Cyelopropachromone
A Pyridocarbazole to Pyridazinocarbazole Rearrangement
Substituent Group Effect During Sulfide ~ Sulfoxide Oxidation
Ring Contraction of a Benzodiazepine
An Indane-1,3-dione Synthesis
An Azepine to Cyclohexadienone Ring Contraction
anthopterin from Pterin 8-Oxide
Fused Dihydro-1,4-dithiins from Chromanones
The "Additive Pummerer Reaction"
An Illustration of the Problem of Artefacts in Natural Product Chemistry
Vinylogy, and a Stereochemical Puzzle
A Simple, High Yielding Route to a Cage Compound
Not all Ketals Hydrolyse Easily in the Expected Manner
From a Tricycle to a Ring Expanded Bicycle
A Flavone from a Chromanone
Thiophene Ylide Rearrangement
A Stepwise 2п + 2п Intermolecular Cycloaddition
Rearrangement of an Aryl Propargyl Ether
The Best Laid Plans
A New Synthesis of Substituted Ninhydrins
Thermal Elimination Reactions Often Fail
The Wrong Choice of Reaction Conditions? How not to Prepare an Acid Chloride
Quantitative Yield Isomerisation of a Xylenol Derivative an Alternative Route to the Starting Material for Problem
Hydride-Induced Rearrangements with Indole Alkaloid Intermediates
An Unusual "Hydrolysis" Product of 2-Nitrosopyridine
A Quinolizine to Indolizine Transformation
S_NHetAr Reactions Often Proceed with Complications
Rearrangement During Recrystallisation
Another Attempt to Reduce a Ketone Goes Wrong
A More Complex Benzocyclobutane to Isochroman-3-one Rearrangement (c.f. Problem 138)
Indoles by Solvometalation Ring Closure
An Unusual - but Inefficient - Synthesis of Methyl
Hydroxynaphthalene-2-carboxylate
Synthesis of a-Arylalkanoic Acids from Acetophenones
Triazene-Triazole-Triazole Interconversions
Reissert Compounds as Precursors to Novel Phthalides
Di-t-butylacetylene does not Cycloadd to 2-Pyrone
A Failed Thorpe-Dieckmann cyclisation: "Obvious" Reactions are not Always Well Behaved
And Can Lead to Remarkable Rearrangements: A Failed Thorpe-Ziegler Cyclisation
A Remarkably Stable Tertiary Alcohol by Solvolysis of a Primary Tosylate
"Anionic Activation" for the Preparation of Fluoroheterocycles
Synthesis of a 5-(2-Quinolyl)pyrimidine
"Obvious" and "Non-Obvious" Pathways to a Highly Substituted Pyridine and Aniline
A 1-Isoquinolone Synthesis
Selective Cleavage of the Mycinose Sugar from the Macrolide Antibiotic Tylosin
Unexpected Formation of an Enamide
Highly Functionalised Furans from 3-Bromochromone
A One-Pot Benzene → Naphthalene Transformation carious
Nucleophilic Substitution Routes from Simple to Complex Phenols
Lewis Acid Catalysed Rearrangement of Humulene 8,9-Epoxide
From a Dihydrofuran to an Indole-3-acetate
Reaction of Fervenulin 4-Oxide with DMAD" The Role of Solvent
Rearrangement of 4-Quinazolinylhydrazines
A Failed Approach to the Oxetan-3-one System
Tricyclics from Furfural
An Ylide-Based Synthesis of 4-Phenylisocoumarin
Model Studies for Mitomycin A Synthesis Lead to a New Preparation of Pyrroloindoles
Formation of N-Cyanofluoren-9-imine from 9-Dinitromethylenefluorene
Methylphenylacetic Acids from Butenolides
Base-Induced Quinoline Rearrangements
The Angucyclines: Rearrangement of Angular to Linear Tetracycles
1,2-Dihydropyridines from 2,3-Dihydro-4-pyridones
The Vitamin K to Vitamin K Oxide Transformation
Rearrangement During Intramolecular Cyclisation to the Indole 4-Position
Quinolone Antibacterials: A New Synthesis
An Efficient Synthesis of Fused 1,3-Dithiol-2-ones
The "Double Functional Group Transformation"" Terminally Unsaturated
Nitriles from 1-Nitrocycloalkenes
Lewis Acid-Catalysed Condensation of Indole with 1,3-Cyclohexanedione
Serendipitous Preparation of a Pyrrole Precursor to Porphyrins
A Chromone Ring Contraction
A Simple Conversion of Hydroquinone to a Benzofuran, but Which Mechanism?
A Remarkable Loss of One Carbon Atom in the Indole Alkaloid Field
A "Non-Obvious" Cycloaddition Reaction
More Radical Cascades and a Formal [2+2+2] Cycloaddition of a Dienyne
LTA-Induced Acetoxylation and Rearrangement of a Phenol
How Cocaine Decomposes at 550~
A Highly Efficient Anilide to Benzimidazole Transformation
The Baeyer-Drewson Synthesis of Indigo
The Marschalk Reaction
A 1,3-Cyclohexanedione to 2-Cyclohexenone Conversion
Reaction of a Steroidal Olefin with Br₂/AgOAc
A Most Unusual Synthesis of Tropones from Phenols
Side-Chain Manipulation with a Purine Derivative" Unexpected Formation of a Thietane
An Isoxazoline to Pyridine N-Oxide Transformation
A Simple Synthesis of the Lignan Carpanone
Cyclopentaquinolines by Tandem Reactions
Epimerisation of Herqueinone
A New Method for Amide Bond Formation
A Benzothiazole from Oxidation of Mammalian Red Hair with
Hydrogen Peroxide
Cyclopentenones from Cyclopentane- 1,3-diones
A New Synthesis of 1- and 2-Chloronaphthalenes by an Annulation Process
From the Diterpene Camosol to the Benzodiazepine Agonist Miltirone
Synthesis of Chiral Phthalimidine Derivatives
Remarkable Rearrangement of a Camphor Derivative
A Failed Attempt to Prepare Benzylidenethiophthalide by the "Obvious" Method
Base-Catalysed Reactions of Highly Hindered Phenols Used as Antioxidants
Oxidative Rearrangement of an Aconitine Derivative
Decomposition of Akuammicine
Extending the Favorskii Reaction
Dihydroxylation/Base Treatment of the Westphalen Ketone
Quantitative Conversion of a Vinylogous Thioamide into a Thiophene
Rearrangements During Synthetic Studies on Carba-Sugars
A Pyrimidine to Pyrazole Transformation
Attempted Diastereocontrol in Synthesis of a Homoallylic Alcohol
Arsonium Ylides for Cyclopropane Synthesis
Pyridoacridines from 4-Quinolones
Imidoyl Radicals in a New Quinoline Synthesis
Electrolytic Fluorinative Ring Expansion Reactions
An Isoxazole to 1,3-Oxazine Transformation
Synthesis of Folate Antimetabolites : A Furan to Pyrrole Transformation
Rearrangement of a Silylacetylenic Ketone
And More Silyl Rearrangements : A Brook-Retro-Brook Sequence
Two Syntheses of Dehydrorotenone
Radical-Induced Decarboxylation of a Lactone
Aryl Azide Thermolysis: "A Series of Rather Involved Rearrangement Reactions"
An Efficient Route to Hexakis(trifluoromethyl)cyclopentadiene
Exploitation of the Boulton-Katritzky Rearrangement: Synthesis of 4,4'-Diamino-3,3'-bifurazan
Rearrangement During Hydrolysis of a Cyclohexadienone
Less Common Sigmatropic Rearrangements: [3,4], [3,5] or even [2,3,2]?
Failure to Construct an Oxetane by S N' Rearrangement
Acid-Catalysed Isomerisation of a Tetraspiroketone