Preface |
Acknowledgments |
Synthesis of [alpha]-Diazocarbonyl Compounds / 1.: |
Introduction / 1.1: |
Acylation of Diazoalkanes / 1.2: |
Preparation of Diazomethane from Diazald |
Preparation of a Diazoketone from an Acid Chloride: Synthesis of 1-Diazo-4-phenyl-2-butanone |
Preparation of a Diazoketone from Mixed Carbonic Anhydrides: Synthesis of N-tert-Butoxycarbonyl-L-Phenylalanyl Diazomethane |
Diazo Transfer Reactions / 1.3: |
Simple Diazo Transfer Reactions / 1.3.1: |
Simple Diazo Transfer Reaction: Synthesis of tert-Butyl [alpha]-Diazoacetoacetate |
Deformylating Diazo Transfer and Related Modifications / 1.3.2: |
Deformylating Diazo Transfer Reaction: Synthesis of 2-Diazocyclohexanone |
Detrifluoroacetylating Diazo Transfer: Synthesis of (E)-1-Diazo-4-Phenyl-3-Buten-2-one |
Effects of Base and Solvent on Diazo Transfer / 1.3.3: |
Direct Diazo Transfer Using 2,4,6-Triisopropyl-phenylsulfonyl Azide: Synthesis of 2-Diazo-5-methoxy-1-tetralone |
Effects of Transfer Reagent on Diazo Transfer and Hazards Evaluation / 1.3.4: |
Synthesis of 4-Dodecylbenzenesulfonyl Azide |
Other Routes to Diazocarbonyl Compounds / 1.4: |
Glyoxylic Acid Chloride p-Toluenesulfonyl-hydrazone: Preparation of Diazoester 158 |
Chemical Modification of Diazocarbonyl Compounds / 1.5: |
Conclusion: Safety and Handling of Diazocarbonyl Compounds / 1.6: |
References / 1.7: |
Catalysts for Metal Carbene Transformations / 2.: |
Electrophilic Addition to Diazo Compounds / 2.1: |
Mechanism of Catalytic Diazo Decomposition. Metal Carbene Generation and Reactions / 2.2: |
Mechanism of Catalytic Diazo Decomposition. Electrophilic Addition by Metal Olefin Complexes / 2.3: |
Copper Catalysts for Diazo Decomposition / 2.4: |
Oxidation States for Copper / 2.4.1: |
Ligands for Copper / 2.4.2: |
Ligand Preparation |
Cobalt Catalysts for Diazo Decomposition / 2.5: |
Palladium Catalysts for Diazo Decomposition / 2.6: |
Rhodium Catalysts for Diazo Decomposition / 2.7: |
Dirhodium (II) Carboxylates / 2.7.1: |
Rhodium(II) Perfluorobutyrate |
Dirhodium(II) Tetrakis[4-tert-butyl-N-benzenesulfonyl-L-prolinate] |
Dirhodium(II) Carboxamidates / 2.7.2: |
Dirhodium(II) Caprolactamate |
Dirhodium(II) Tetrakis[methyl 2-oxooxazolidine-4(S)-carboxylate], Rh[subscript 2](4S-MEOX)[subscript 4] |
Hexarhodium Hexadecacarbonyl / 2.7.3: |
Dirhodium(II) Phosphates and Orthometallated Phosphines / 2.7.4: |
Rhodium(III) Porphyrins / 2.7.5: |
Ruthenium Catalysts for Diazo Decomposition / 2.8: |
Other Transition Metals as Catalysts for Diazo Decomposition / 2.9: |
Osmium / 2.9.1: |
Iron / 2.9.2: |
Platinum and Nickel / 2.9.3: |
The Chromium Triad / 2.9.4: |
Metal Carbenes as Stoichiometric Reagents / 2.10: |
Insertion Reactions / 2.11: |
Catalytic Intermolecular Carbon-Hydrogen Insertion Reactions / 3.1: |
Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions: General Considerations / 3.2: |
Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoketones: Regioselectivity for Cyclopentanone Formation / 3.3: |
Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoketones and Diazoesters: Diastereoselectivity and Synthetic Applications / 3.4: |
Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoacetates: Lactone Formation / 3.5: |
Catalytic Dinitrogen Extrusion from l-(--)-Menthyl Diazoacetoacetate |
Catalytic Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoacetamides: Lactam Formation / 3.6: |
Catalyst-Dependent Chemoselectivity and Regioselectivity for Carbon-Hydrogen Insertion / 3.7: |
Enantioselectivity in Intramolecular Carbon-Hydrogen Insertion Reactions / 3.8: |
Synthesis of (+)-Arctigenin |
Synthesis of (4R,5R)-(+)-2-Deoxyxylolactone |
Diastereoselection and Regioselection in Carbon-Hydrogen Insertion Reactions Promoted by Chiral Catalysts / 3.9: |
Diastereoselection in Carbon-Hydrogen Insertion Reactions Controlled with the Use of Chiral Auxiliaries / 3.10: |
Silicon-Hydrogen and Related Insertion Reactions / 3.11: |
Intermolecular Cyclopropanation and Related Addition Reactions / 3.12: |
Cyclopropanation with Diazomethane / 4.1: |
Cyclopropanation Reactions with Diazocarbonyl Compounds. General / 4.2: |
Intermolecular Cyclopropanation Reactions of Diazocarbonyl Compounds. Diastereoselectivity / 4.3: |
2,6-Di-tert-butyl-4-methylphenyl Diazoacetate (BDA) |
Intermolecular Cyclopropanation Reactions of Diazocarbonyl Compounds. Regioselectivity and Relative Reactivities / 4.4: |
Mechanism of Cyclopropanation. Stereochemistry of Cyclopropane Formation / 4.5: |
Intermolecular Cyclopropanation Reactions of Diazocarbonyl Compounds. Enantioselectivity / 4.6: |
Salicylaldimine-Copper Catalysts / 4.6.1: |
Semicorrin-Copper Catalysts / 4.6.2: |
bis(Oxazoline)-Copper Catalysts / 4.6.3: |
Pyridine-Ligated Copper Catalysts / 4.6.4: |
Other Chiral Copper Catalysts / 4.6.5: |
Chiral Dirhodium(II) Carboxylates / 4.6.6: |
Chiral Dirhodium(II) Carboxamidates / 4.6.7: |
Other Chiral Rhodium Catalysts / 4.6.8: |
Pybox-Ruthenium Catalysts / 4.6.9: |
Cobalt Catalysts / 4.6.10: |
Donor-Acceptor Cyclopropanes in Organic Synthesis / 4.7: |
Vinyldiazoacetates--Intermolecular Annulation Reactions / 4.8: |
Formal [3+4]-Cycloaddition / 4.8.1: |
Formal [3+2]-Cycloaddition / 4.8.2: |
1,3-Dipolar Ketocarbene Addition / 4.9: |
Intermolecular Cyclopropanation and Subsequent Reactions in Synthesis / 4.10: |
Cyclopropenation of Alkynes / 4.11: |
Aziridination / 4.12: |
Addition to Imines / 4.12.1: |
Nitrene Addition to Alkenes / 4.12.2: |
Intramolecular Cyclopropanation and Related Addition Reactions / 4.13: |
Intramolecular Cyclopropanation of Diazoketones / 5.1: |
Vinylcyclopropylcarbonyl Compounds in Organic Synthesis / 5.2: |
Intramolecular Cyclopropanation of Diazoesters and Diazoamides / 5.3: |
Regioselectivity and Chemoselectivity in Intramolecular Cyclopropanation Reactions / 5.4: |
Enantioselective Intramolecular Cyclopropanation Reactions / 5.5: |
Synthesis of (1R,5S)-(--)-6,6-Dimethyl-3-oxabicyclo-[3.1.0]hexan-2-one |
Synthesis of (1S,5R)-(+)-3,6,6-Trimethyl-3-azabicyclo-[3.1.0]hexan-2-one |
Diastereocontrol in Intramolecular Cyclopropanation Reactions / 5.6: |
Macrocyclic Cyclopropanation / 5.7: |
Intramolecular Cyclopropenation Reactions: Tandem/Cascade Processes / 5.8: |
Cycloaddition and Substitution Reactions with Aromatic and Heteroaromatic Compounds / 5.9: |
Intermolecular Reactions with Benzene and its Derivatives / 6.1: |
Diazoesters / 6.1.1: |
Diazoketones / 6.1.2: |
Intramolecular Cycloaddition Reactions with Benzene Derivatives / 6.2: |
Diazoketone Cyclization onto a Benzene Ring: 3,4-Dihydro-1(2H)-Azulenone [1(2H)-Azulenone, 3,4-dihydro-] / 6.2.1: |
Diazoesters and Diazoamides / 6.2.2: |
Chemoselectivity in Aromatic Cycloaddition / 6.2.3: |
Asymmetric Synthesis in Aromatic Cycloaddition / 6.2.4: |
Substitution Reactions with Aromatic Compounds / 6.3: |
Rhodium(II) Acetate-Catalyzed Decomposition of 2-Diazo-3-oxobutanamides |
Chemoselectivity in Aromatic Substitution / 6.3.1: |
Asymmetric Synthesis in Aromatic Substitution / 6.3.2: |
Cycloaddition and Substitution Reactions with Heterocyclic Aromatic Compounds / 6.4: |
Furans / 6.4.1: |
Reaction of EDA with Furan |
Pyrroles / 6.4.2: |
Thiophenes / 6.4.3: |
Generation and Reactions of Ylides from Diazocarbonyl Compounds / 6.5: |
Formation of Sulfur Ylides / 7.1: |
Formation of Stable Sulfonium and Sulfoxonium Ylides from Diazocarbonyl Precursors / 7.2.1: |
Intermolecular Formation of Sulfur Ylides and Subsequent Reactions / 7.2.2: |
Reaction of 2-Phenyl-1,3-dithiane with EDA |
Intramolecular Formation of Sulfur Ylides and Subsequent Reactions / 7.2.3: |
[beta]-Elimination and Related [1,4] Rearrangement / 7.2.4: |
Chemo- and Stereoselectivity in Sulfur Ylide Formation and Subsequent Rearrangement / 7.2.5: |
Formation of Oxonium Ylides / 7.3: |
Intermolecular Formation of Oxonium Ylides and Subsequent Reactions / 7.3.1: |
Intramolecular Formation of Oxonium Ylides and Subsequent Reactions / 7.3.2: |
[2,3]-Sigmatropic Rearrangement of Cyclic Oxonium Ylide: Synthesis of 8-Chloro-5,7-dimethoxy-2-carbomethoxy-2-[1-(S)- methyl-2-butenyl]benzofuran-3-one |
Chemo-, Diastereo-, and Enantioselectivity in Oxonium Ylide Formation / 7.3.3: |
Formation of Nitrogen Ylides from Diazocarbonyl Compounds / 7.4: |
Intermolecular Formation of Nitrogen Ylides and Subsequent Reactions / 7.4.1: |
Intramolecular Formation of Nitrogen Ylides and Subsequent Reactions / 7.4.2: |
Formation of Carbonyl Ylides from Diazocarbonyl Compounds / 7.5: |
Intermolecular Carbonyl Ylide Formation and Subsequent Reactions / 7.5.1: |
Intramolecular Carbonyl Ylide Formation and Subsequent Reactions / 7.5.2: |
Intramolecular Carbonyl Ylide Formation and Subsequent 1,3-Dipolar Cycloaddition Reaction: Synthesis of 6,8-Dioxabicyclo[3.2.1]octane Ring Systems |
Chemoselectivity in Carbonyl Ylide Formation / 7.5.3: |
Formation of Thiocarbonyl Ylides from Diazocarbonyl Compounds / 7.6: |
X-H Insertion Reactions of Diazocarbonyl Compounds (X = N, O, S, Se, P, Halogen) / 7.7: |
N-H Insertion / 8.1: |
Intermolecular N-H Reactions / 8.2.1: |
Intramolecular N-H Insertion / 8.2.2: |
Asymmetric N-H Insertion / 8.2.3: |
O-H Insertion with Water, Alcohols, and Phenols / 8.3: |
Intermolecular O-H Insertion / 8.3.1: |
2-Isopropoxycyclohexanone |
Intramolecular O-H Insertion / 8.3.2: |
Asymmetric O-H Insertion / 8.3.3: |
O-H Insertion Reactions with Carboxylic Acids, Carboxylic Esters, and Sulfonic Acids / 8.4: |
(S)-3-N-(Phthalimido)-4-phenyl-1-(methane-sulfonyloxy)butan-2-one |
S-H Insertion / 8.5: |
2-(Phenylthio)-6-phenyl-3-hexanone |
Se-H Insertion / 8.6: |
P-H Insertion / 8.7: |
X-H Insertion (X = Halogen) / 8.8: |
The Wolff Rearrangement and Related Reactions / 8.9: |
The Arndt-Eistert Homologation / 9.1: |
Ethyl 1-Naphthylacetate |
3(S)-Methyl-3-(N-tert-butoxycarbonylamino)-6-(N-bis-benzyloxycarbonyl guanidyl)hexanoate |
Protected Homopeptide |
Ring Contraction via the Wolff Rearrangement / 9.2: |
Formation and Photochemical Wolff Rearrangement of Cyclic [alpha]-Diazoketones: D-Norandrost-5-en-3[beta]-ol-16-carboxylic Acids |
The Wolff Rearrangement with Cycloaddition Reactions / 9.3: |
The Vinylogous Wolff Rearrangement / 9.4: |
Miscellaneous Applications of the Wolff Rearrangement / 9.5: |
Conclusions / 9.6: |
Reactions of [alpha]-Diazocarbonyl Compounds with Aldehydes and Ketones / 9.7: |
Base Promoted Reactions of [alpha]-Diazocarbonyl Compounds with Aldehydes and Ketones / 10.1: |
Base-Promoted Reactions of [alpha]-Diazocarbonyl Compounds with Aldehydes: Synthesis of (N-Butoxy-carbonyl-L-Phenylalanyl)-Methyl Phenyl Ketone |
Acid-Catalyzed Reactions of [alpha]-Diazocarbonyl Compounds with Aldehydes / 10.3: |
Synthesis of [beta]-Dicarbonyl Compounds via Tin(II) Chloride-Catalyzed Reaction: Conversion of Hydrocinnamaldehyde into Ethyl 3-Oxo-5-phenylvalerate |
Synthesis of Tetrahydrofurans / 10.4: |
Tetrahydrofuran Annulation with [beta]-p-Methoxybenzyl Pivalaldehyde and Ethyl Diazoacetate: Synthesis of Substituted Tetrahydrofuran 14 |
Olefination of Aldehydes and Ketones with Diazocarbonyl Compounds / 10.5: |
Acid-Catalyzed Reactions of [alpha]-Diazocarbonyl Compounds with Ketones / 10.6: |
Homologation of Cyclobutanone Ring with Ethyl Diazoacetate: Synthesis of Methyl (2S,3aR,6aS)-1,2,3,3a,4,5,6,6a-Octahydro-2-methyl-4-oxopentalene-2-carboxylate |
Acid-Promoted Cyclization of Unsaturated and Aromatic Diazo Ketones / 10.7: |
Cyclization of [gamma, delta]-Unsaturated Diazoketones / 11.1: |
Cyclization of [beta, gamma]-Unsaturated Diazoketones / 11.3: |
Intramolecular Alkylation of Diazoketones through Aryl Participation / 11.4: |
Ar[subscript 1]-5 Participation in the Cyclization of Aromatic Diazoketones / 11.4.1: |
Ar[subscript 1]-6 Participation in the Cyclization of Aromatic Diazoketones / 11.4.2: |
Ar[subscript 1]-4 Cyclization in the Cyclization of Aromatic Diazoketones / 11.4.3: |
Synthesis of Heterocycles by Acid-Promoted Cyclization of [alpha]-Diazocarbonyl Compounds / 11.5: |
Miscellaneous Diazocarbonyl Reactions / 11.6: |
Oxidation of Diazocarbonyl Compounds / 12.1: |
Oxidation of N-Benzyloxycarbonyl-L-phenylalanyl diazomethane with Dimethyldioxirane. Preparation of an N-Protected Amino Glyoxal Hydrate |
[beta]-Hydride Elimination / 12.3: |
Preparation of Methyl (Z)-2-Undecenoate from Methyl 2-Diazoundecanoate |
X-Y Insertion Reactions / 12.4: |
X-Y = The Halogens / 12.4.1: |
X-Y = Arenesulfonyl Halides (ArS-X) / 12.4.2: |
X-Y = Areneselenyl Halides and Diphenyl Diselenide (ArSe-X) / 12.4.3: |
Preparation of 2-Phenylselenyl-2-cyclohexen-1-one from 2-Diazocyclohexanone |
X-Y = Trialkylboranes (R-BR[subscript 2]) / 12.4.4: |
Dimerization Reactions / 12.5: |
Diazocarbonyl Compounds as 1,3-Dipoles in [3+2] Cycloaddition Reactions / 12.6: |
Index / 12.7: |