Volume 4: Compounds of Group 15 (As, Sb, Bi) and Silicon Compounds

Transcription

1 XV Volume 4: Compounds of Group 15 (As, Sb, Bi) and Silicon Compounds 4.4 ProductClass 4: Silicon Compounds Silyl Hydrides R. W. Clark and S. L. Wiskur Silyl Hydrides Synthesis of Silyl Hydrides Method 1: From Inorganic Silanes Method 2: From Alkyl- orarylsilanes Method 3: From Silyl Halides Method 4: From Silyl Ethers Method 5: From Other Silyl Hydrides by Monohalogenation or Deuterium Exchange Applications of Silyl Hydrides in Organic Synthesis Method 1: Hydrosilylation of Alkenes, Alkynes, and Related Compounds Method 2: Silyl Hydrides as Reducing Agents Method 3: Dehydrogenative Silylation Vinylsilanes E. A. Andersonand D. S. W. Lim Vinylsilanes Vinylmetal Addition to Silane Electrophiles Method 1: Addition to Chlorosilanes Method 2: Addition to Cyclic Siloxanes Hydrosilylation of Alkynes Method 1: Transition-Metal-Catalyzed b-hydrosilylation of Terminal Alkynes To Give E-Vinylsilanes Variation 1: Platinum Catalysis Variation 2: Rhodium Catalysis Variation 3: PalladiumCatalysis Variation 4: Iridium Catalysis Method 2: Transition-Metal-Catalyzed b-hydrosilylation of Terminal Alkynes To Give Z-Vinylsilanes Variation 1: Ruthenium Catalysis Variation 2: Rhodium Catalysis... 75

2 XVI Variation 3: Iridium Catalysis Method 3: Transition-Metal-Catalyzed a-hydrosilylation of Terminal Alkynes Variation 1: Ruthenium Catalysis Variation 2: Platinum Catalysis Method 4: Transition-Metal-Catalyzed syn Hydrosilylation of Internal Alkynes Variation 1: Platinum Catalysis Variation 2: PalladiumCatalysis Method 5: Transition-Metal-Catalyzed anti Hydrosilylation of Internal Alkynes Method 6: Lewis Acid Catalyzed Hydrosilylation Method 7: Radical Hydrosilylation Silylmetalation of Alkynes Method 1: Silylcupration Variation 1: Silylcupration Using Silyllithium Reagents Variation 2: Silylcupration Using Silylboronic Ester Reagents Method 2: Copper-Catalyzed Silylmetalation Method 3: Silylzincation Method 4: Silylrhodation Addition to Alkynylsilanes Method 1: Hydrogenation Method 2: Hydrometalation Variation 1: HydrometalationFollowed by Protodemetalation Variation 2: HydrometalationFollowed by Halogenation Variation 3: HydrometalationFollowed by Alkylation Method 3: Carbometalation Intermolecular Coupling of Alkynylsilanes Method 1: Ruthenium-Catalyzed Alder-Ene Reaction Method 2: Reductive Coupling Method 3: Enyne Cross Metathesis Ring-Closing Metathesis of a-substituted Vinylsilanes Dehydrogenative Silylation of Alkenes Method 1: Reaction with Silanes Method 2: Reaction with Halosilanes or Silyl Trifluoromethanesulfonates Method 3: Transfer Silylation Method 4: Reaction with Siletanes Carbometalation of Vinylsilanes Method 1: Heck Reaction with Aryl Halides Method 2: Heck-Type Reaction with Benzonitriles Method 3: Iron-Catalyzed Oxidative Arylation Addition to Carbonyl Compounds Method 1: Reaction with (Dihalomethyl)silane Reagents

3 XVII Method 2: Reaction with Disilylmethyllithium Reagents Method 3: Reaction with (Halomethyl)silane Reagents Method 4: Reaction with (a-silylallyl)borane Reagents Rearrangements Method 1: Gold-Catalyzed RearrangementofAllyl(alkynyl)silanes Method 2: Rearrangementof(a-Hydroxypropargyl)silanes Method 3: RearrangementofSilyl Allenoates Synthesis of Cyclic Vinylsilanes Method 1: IntramolecularHydrosilylation of Alkynes Variation 1: Metal-Catalyzed syn-exo Hydrosilylation Variation 2: Metal-Catalyzed anti-exo Hydrosilylation Variation 3: Metal-Catalyzed endo-hydrosilylation Variation 4: Base-Promoted Hydrosilylation Method 2: Cyclization of Vinylsilanes Variation 1: By Ring-Closing Metathesis with Terminal Vinylsilanes Variation 2: By Silylvinylation Method 3: Cyclization of Alkynylsilanes Variation 1: By Ring-Closing Enyne Metathesis Variation 2: By Reductive Coupling of Alkynylsilanes Variation 3: By Gold-Catalyzed Cyclization Variation 4: By Semihydrogenation Method 4: Three-Component Coupling Method 5: Ring Contraction of Cyclic Vinylsilanes Synthesis from Acylsilanes Synthesis from Allenes Method 1: Hydrosilylation Method 2: Silylmetalation Volume 31: Arene X (X =Hal, O, S, Se,Te, N, P) 31.1 ProductClass 1: Fluoroarenes Fluoroarenes A. Harsanyiand G. Sandford Fluoroarenes Synthesis of Fluoroarenes Synthesis by Substitution of Hydrogen Method 1: Reaction with Hydrogen Fluoride Pyridine Complex Method 2: Reaction with Silver(II) Fluoride Method 3: Reaction with Fluorinating Agents Mediated by Transition- Metal Catalysts

4 XVIII Synthesis by Substitution of Organometallic Groups Method 1: Substitution ofboronic Acids and Esters Variation 1: Reaction with Silver(I) Trifluoromethanesulfonate and Selectfluor Variation 2: Reaction with AcetylHypofluorite Variation 3: Palladium-Catalyzed Fluorodeboronation Variation 4: Copper-Catalyzed Fluorodeboronation Synthesis by Substitution of Halogens Method 1: Reaction with Anhydrous Tetrabutylammonium Fluoride Method 2: Reactions Catalyzed bytransition Metals Variation 1: Palladium-Catalyzed Reactions Variation 2: Copper-Catalyzed Reactions Synthesis by Substitution of Nitrogen Synthesis by Substitution of Oxygen Method 1: Palladium-Catalyzed Displacement of TrifluoromethanesulfonatebyCesium Fluoride Method 2: Deoxyfluorination Using PhenoFluor ProductClass 2: Chloroarenes Chloroarenes S. P. Stanforth Chloroarenes Synthesis of Chloroarenes Synthesis by Substitution Method 1: Electrophilic Chlorination Variation 1: Of Phenols and Anisoles Variation 2: Of Anilines, Acetanilides, and Related Compounds Variation 3: Of Benzeneand Alkylbenzene Derivatives Variation 4: Of Electron-Deficient Benzene Derivatives Method 2: Substitution ofboron Method 3: Substitution ofbromine Synthesis by Addition Elimination Applications of ChloroarenesinOrganic Synthesis Method 1: Cross-Coupling Reactions Variation 1: Synthesis of Biaryls Variation 2: Synthesis of Arylalkenes Variation 3: Synthesis of Arylalkynes Variation 4: Synthesis of Arylalkanes Variation 5: Carbonylation and Cyanation Reactions Variation 6: Metal-CatalyzedHeterosubstitution Reactions

5 XIX 31.3 ProductClass 3: Bromoarenes Bromoarenes S. P. Stanforth Bromoarenes Synthesis of Bromoarenes Synthesis by Substitution Method 1: Electrophilic Bromination Variation 1: Of Phenols and Anisoles Variation 2: Of Anilines, Acetanilides, and Related Compounds Variation 3: Of Benzeneand Alkylbenzene Derivatives Variation 4: Of Electron-Deficient Benzene Derivatives Variation 5: Of Arylboronates Method 2: Synthesis from Organometallics Variation 1: From Arylboronates Method 3: Substitution ofatrifluoromethanesulfonate Group Applications of Bromoarenes in Organic Synthesis Method 1: Cross-Coupling Reactions Variation 1: Synthesis of Biaryls Variation 2: Synthesis of Arylalkenes Variation 3: Synthesis of Arylalkynes Variation 4: Synthesis of Arylalkanes Variation 5: Carbonylation and Cyanation Reactions Variation 6: Metal-CatalyzedHeterosubstitution Reactions Variation 7: Borylation Reactions Variation 8: Phosphonylation Reactions Variation 9: Transhalogenation Reactions Method 2: Hydrodebromination Reactions ProductClass 4: Aryl Iodine Compounds Hypervalent Iodoarenes and Aryliodonium Salts V. V. Zhdankin Hypervalent Iodoarenes and Aryliodonium Salts Synthesis of Hypervalent Iodoarenes and Aryliodonium Salts Synthesis by Oxidative AdditiontoIodoarenes Method 1: Iodylarenes by Oxidation of Iodoarenes Variation 1: Acyclic Iodylarenes Variation 2: Cyclic Iodylarenes Variation 3: Polymer-Supported Iodylarenes Method 2: (Difluoroiodo)arenesbyFluorination of Iodoarenes

6 XX Variation 1: (Difluoroiodo)arenes by One-PotSynthesis from Arenes Method 3: (Dichloroiodo)arenes by ChlorinationofIodoarenes Method 4: [Bis(acyloxy)iodo]arenes by Oxidation of Iodoarenes in the Presence of acarboxylic Acid Method 5: Aryliodine(III) Sulfonates by Oxidation of Iodoarenes in the Presence of asulfonic Acid Synthesis by LigandExchange of Hypervalent Iodine Compounds Method 1: 1-Oxo-1-(tosyloxy)-1H-1l 5 -benzo[d][1,2]iodoxol-3-one from 2-Iodoxybenzoic Acid by Exchange with 4-Toluenesulfonic Acid Method 2: [Bis(acyloxy)iodo]arenes from Other [Bis(acyloxy)iodo]arenes by Exchange with Carboxylic Acids Method 3: Phenyliodine(III) Sulfate from (Diacetoxyiodo)benzene Method 4: Iodosylarenes by Hydrolysis of [Bis(acyloxy)iodo]arenes Method 5: Aryliodine(III) Amides from (Acyloxyiodo)arenes Method 6: Alkynyl(aryl)iodonium Salts from HypervalentIodoarenes Variation 1: Alkynyl(aryl)iodonium Tetrafluoroborates Variation 2: Alkynyl(aryl)iodonium Trifluoroacetates Variation 3: Alkynyl(aryl)iodonium Organosulfonates Variation 4: 1-Alkynylbenziodoxoles Method 7: Aryl-and Hetaryliodonium Salts from HypervalentIodoarenes Variation 1: Aryliodonium Tetrafluoroborates Variation 2: Aryl-and Hetaryliodonium Sulfonates Variation 3: Aryliodonium Halides Variation 4: 1-Arylbenziodoxoles Method 8: 1-(Trifluoromethyl)benziodoxoles by Trifluoromethylation of Other Benziodoxoles Method 9: Aryliodonium Ylides from (Diacetoxyiodo)arenes Method 10: Aryliodonium Imides from (Diacetoxyiodo)arenes Applications of Hypervalent Iodoarenes and Aryliodonium Salts in Organic Synthesis Preparation of Products with anew C-CBond Method 1: Alkynylation Using 1-Alkynylbenziodoxoles Method 2: Arylation Using Diaryliodonium Salts Method 3: Trifluoromethylation Using (Trifluoromethyl)benziodoxoles Method 4: Reactions of Aryliodonium Ylides Preparation of Products with anew C-F Bond Method 1: a-fluorination of Carbonyl Compounds Method 2: Fluorination of Aromatic Compounds Preparation of Products with anew C-Cl Bond Method 1: Chlorination of Unsaturated Compounds Preparation of Products with anew C-IBond Method 1: Oxidative Iodination Using Hypervalent Iodoarenes

7 XXI Oxidations and Oxidative Rearrangements Reactions with Iodine(V) Reagents Method 1: Oxidations with Iodylarenes Method 2: Iodine(V)-Catalyzed Oxidations Variation 1: Catalytic Oxidation of Alcohols to Carbonyl Compounds Variation 2: Catalytic Oxidation at the Benzylic Position Variation 3: Catalytic Preparation of a,b-unsaturated Carbonyl Compounds Reactions with Iodine(III) Reagents Method 1: 2,2,6,6-Tetramethylpiperidin-1-oxyl-Catalyzed Oxidation of Alcohols Method 2: Diacetoxylation ofalkenes Method 3: Oxidative Dearomatization of Phenols and Phenol Ethers Variation 1: Oxidation of 4-Substituted Phenols Variation 2: Oxidation of 2-Substituted Phenols Method 4: Iodine(III)-Catalyzed Oxidations Variation 1: Catalytic a-functionalization of Carbonyl Compounds Variation 2: Catalytic Lactonization Reactions Variation 3: Catalytic StereoselectiveDiacetoxylationofAlkenes Variation 4: Catalytic Oxidative Cleavage of Alkenes and Alkynes Variation 5: Catalytic Spirocyclization of Aromatic Substrates Preparation of Products with anew C-NBond Method 1: Azidations with Iodine(III) Reagents Method 2: Aminations with Iodine(III) Reagents Method 3: Reactions of Aryliodonium Imides Variation 1: C-HAmidation Variation 2: Aziridination of Alkenes Oxidations at Nitrogen Method 1: HypervalentIodoarenes as Reagents for Hofmann Rearrangement Variation 1: HypervalentIodine Catalyzed Hofmann Rearrangement Method 2: HypervalentIodoarenes as Reagents for Generation of Nitrile Oxides from Oximes Variation 1: Synthesis of Dihydroisoxazoles via Hypervalent Iodine Catalyzed Generation of Nitrile Oxides ProductClass 41: Arylphosphine Oxides Arylphosphine Oxides and Heteroatom Derivatives O. M. Demchuk, M. Stankevič,and K. M. Pietrusiewicz Arylphosphine Oxides and Heteroatom Derivatives Arylphosphine Oxides Synthesis of Arylphosphine Oxides

8 XXII Method 1: Oxidation of Phosphines and Derivatives Variation 1: Oxidation with Dioxygen or Air Variation 2: Catalytic Oxidation Variation 3: Oxidation with Peroxides Variation 4: Photooxidation Variation 5: Oxidation with MiscellaneousOxidants Variation 6: Oxidation of Chalcogen Phosphine Derivatives and Phosphine Boranes Method 2: Addition of SecondaryPhosphine Oxides to Unsaturated Bonds Variation 1: Addition to Unsaturated Carbon-Carbon Bonds Variation 2: Addition to Imines Variation 3: Addition to Carbonyl Compounds Variation 4: Conjugate Addition to Activated Alkenes Method 3: Nucleophilic Substitution at the Phosphorus Atom Variation 1: P-XBond Cleavage (X =Halogen) Variation 2: P-O Bond Cleavage Variation 3: P-CBond Cleavage Variation 4: Hydrolysis of Phosphonium Salts Variation 5: Electrophilic Aromatic Substitution Method 4: Nucleophilic Substitution with Phosphorus Nucleophiles Variation 1: Michaelis Becker Reactions Variation 2: Michaelis Arbuzov Reactions Method 5: Transition-Metal-Mediated P-CBond Formation Variation 1: Copper-Mediated Reactions Variation 2: Nickel-Mediated Reactions Variation 3: Palladium-Mediated Reactions Variation 4: Other Metal-Mediated Reactions Method 6: Other Reactions Variation 1: Phosphinylation of Ortho Esters Variation 2: Manganese(III)-Mediated Free-Radical Phosphinylation Variation 3: Palladium-Catalyzed Intramolecular Dehydrogenative Cyclization Variation 4: Reaction of Elemental Phosphorus Variation 5: The Wittig Reaction Variation 6: The Appel Reaction Variation 7: The Mitsunobu Reaction Method 7: Modification of Phosphine Oxides without Substitution at Phosphorus Variation 1: Monoreduction of Bisphosphine Dioxides Variation 2: Deprotonation Directed by the P=O Group Variation 3: Nucleophilic Aromatic Substitution Promoted by the P=O Group Variation 4: Alkene Metathesis Variation 5: Cycloaddition Reactions Variation 6: Annulation Reactions Variation 7: Cross-Coupling Reactions

9 XXIII Applications of Arylphosphine Oxides in Organic Synthesis Arylphosphine Sulfides Synthesis of Arylphosphine Sulfides Method 1: Sulfuration of Phosphines Variation 1: Using Elemental Sulfur Variation 2: Using Polysulfide Reagents Variation 3: Using Other Sulfur Sources Variation 4: Via Sulfuration of Phosphine Borane Species Variation 5: Via Sulfuration of Other Chalcogen Phosphine Derivatives Method 2: Addition of SecondaryPhosphine Sulfides to Unsaturated Bonds Variation 1: Addition to Carbonyl Compounds Variation 2: Addition to Alkenes Variation 3: Conjugate AdditiontoActivated Alkenes Method 3: Nucleophilic Substitution with Phosphorus Nucleophiles Variation 1: Transition-Metal-MediatedSubstitution Variation 2: Thio-Michaelis Arbuzov Reactions Method 4: Nucleophilic Substitution at the Phosphorus Atom Variation 1: P-XBond Cleavage (X =Halogen) Variation 2: P-S Bond Cleavage Variation 3: P-CBond Cleavage Variation 4: P-O Bond Cleavage Variation 5: Solvolysis of Phosphorus(V) Compounds Method 5: Other Reactions Variation 1: Reaction of Sulfides with Elemental Phosphorus Variation 2: Cycloaddition of Strained Cyclic Phosphine Sulfides with Dienes Variation 3: Wittig Reaction with Thiocarbonyl Compounds Variation 4: Reaction of Ylides with Elemental Sulfur and with Thiiranes Variation 5: Cycloaddition of (Alkylsulfanyl)(chloro)phosphines Variation 6: Reaction of Butadienylphosphine Sulfides Method 6: Modification of Phosphine Sulfides without Substitution at Phosphorus Variation 1: a-and ortho-deprotonation Variation 2: Cycloaddition Reactions Variation 3: Annulation Reactions Applications of Arylphosphine Sulfides in Organic Synthesis Arylphosphine Selenides Synthesis of Arylphosphine Selenides Method 1: Selenation of Free Phosphines with Elemental Selenium Method 2: Other Methods Applications of Arylphosphine Selenides in Organic Synthesis

10 XXIV Aryl(imino)phosphoranes Synthesis of Aryl(imino)phosphoranes Method 1: The Staudinger Reaction of Free Phosphines and Azides Method 2: Synthesis via Aminophosphonium Salts Applications of Aryl(imino)phosphoranes in Organic Synthesis Volume 35: Chlorine, Bromine, and Iodine 35.2 ProductClass 2: One Saturated Carbon Bromine Bond Synthesis by Addition across C=C Bonds G. Dagousset and G. Masson Synthesis by Addition across C=C Bonds Method 1: Hydroxy- and Alkoxybromination of Alkenes Method 2: Aminobromination of Alkenes Method 3: Azidobromination ofalkenes Method 4: Phosphobromination of Alkenes Method 5: Catalytic Enantioselective Syntheses Variation 1: Bromination of Alkenes Variation 2: Hydroxy- and Alkoxybromination of Alkenes Variation 3: Aminobromination of Alkenes Author Index Abbreviations