Science of Synthesis Knowledge Updates 2015 Vol. 1 E-Book

• Herausgeber: Thieme
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1076

Veröffentlichungsjahr: 2015

Beschreibung

The Science of Synthesis Editorial Board, together with the volume editors and authors, is constantly reviewing the whole field of synthetic organic chemistry as presented in Science of Synthesis and evaluating significant developments in synthetic methodology. Four annual volumes updating content across all categories ensure that you always have access to state-of-the-art synthetic methodology.

Leseprobe

Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes:

Methods critically evaluated by leading scientists

Background information and detailed experimental procedures

Schemes and tables which illustrate the reaction scope

Preface

As the pace and breadth of research intensifies, organic synthesis is playing an increasingly central role in the discovery process within all imaginable areas of science: from pharmaceuticals, agrochemicals, and materials science to areas of biology and physics, the most impactful investigations are becoming more and more molecular. As an enabling science, synthetic organic chemistry is uniquely poised to provide access to compounds with exciting and valuable new properties. Organic molecules of extreme complexity can, given expert knowledge, be prepared with exquisite efficiency and selectivity, allowing virtually any phenomenon to be probed at levels never before imagined. With ready access to materials of remarkable structural diversity, critical studies can be conducted that reveal the intimate workings of chemical, biological, or physical processes with stunning detail.

The sheer variety of chemical structural space required for these investigations and the design elements necessary to assemble molecular targets of increasing intricacy place extraordinary demands on the individual synthetic methods used. They must be robust and provide reliably high yields on both small and large scales, have broad applicability, and exhibit high selectivity. Increasingly, synthetic approaches to organic molecules must take into account environmental sustainability. Thus, atom economy and the overall environmental impact of the transformations are taking on increased importance.

The need to provide a dependable source of information on evaluated synthetic methods in organic chemistry embracing these characteristics was first acknowledged over 100 years ago, when the highly regarded reference source Houben–Weyl Methoden der Organischen Chemie was first introduced. Recognizing the necessity to provide a modernized, comprehensive, and critical assessment of synthetic organic chemistry, in 2000 Thieme launched Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. This effort, assembled by almost 1000 leading experts from both industry and academia, provides a balanced and critical analysis of the entire literature from the early 1800s until the year of publication. The accompanying online version of Science of Synthesis provides text, structure, substructure, and reaction searching capabilities by a powerful, yet easy-to-use, intuitive interface.

From 2010 onward, Science of Synthesis is being updated quarterly with high-quality content via Science of Synthesis Knowledge Updates. The goal of the Science of Synthesis Knowledge Updates is to provide a continuous review of the field of synthetic organic chemistry, with an eye toward evaluating and analyzing significant new developments in synthetic methods. A list of stringent criteria for inclusion of each synthetic transformation ensures that only the best and most reliable synthetic methods are incorporated. These efforts guarantee that Science of Synthesis will continue to be the most up-to-date electronic database available for the documentation of validated synthetic methods.

Also from 2010, Science of Synthesis includes the Science of Synthesis Reference Library, comprising volumes covering special topics of organic chemistry in a modular fashion, with six main classifications: (1) Classical, (2) Advances, (3) Transformations, (4) Applications, (5) Structures, and (6) Techniques. Titles will include Stereoselective Synthesis, Water in Organic Synthesis, and Asymmetric Organocatalysis, among others. With expert-evaluated content focusing on subjects of particular current interest, the Science of Synthesis Reference Library complements the Science of Synthesis Knowledge Updates, to make Science of Synthesis the complete information source for the modern synthetic chemist.

The overarching goal of the Science of Synthesis Editorial Board is to make the suite of Science of Synthesis resources the first and foremost focal point for critically evaluated information on chemical transformations for those individuals involved in the design and construction of organic molecules.

Throughout the years, the chemical community has benefited tremendously from the outstanding contribution of hundreds of highly dedicated expert authors who have devoted their energies and intellectual capital to these projects. We thank all of these individuals for the heroic efforts they have made throughout the entire publication process to make Science of Synthesis a reference work of the highest integrity and quality.

The Editorial Board

July 2010

E. M. Carreira (Zurich, Switzerland)

C. P. Decicco (Princeton, USA)

A. Fuerstner (Muelheim, Germany)

G. A. Molander (Philadelphia, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

M. Shibasaki (Tokyo, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Abstracts

4.4.4.8 Silyl Hydrides

R. W. Clark and S. L. Wiskur

This chapter is an update to the earlier article in Science of Synthesis (Section 4.4.4) covering the synthesis and use of silyl hydrides. Recent advances in synthetic preparations of silyl hydrides are explored, as well as the use of silyl hydrides for hydrosilylation, reduction, and dehydrogenative silylation.

Keywords: silyl hydrides • silanes • organosilanes • chiral silanes • hydrosilylation • dehydrogenative silylation • reduction

4.4.34.35 Vinylsilanes

E. A. Anderson and D. S. W. Lim

This chapter is an update to the earlier Science of Synthesis contribution (Section 4.4.34) describing methods for the synthesis of vinylsilanes. It focuses on the literature published in the period 2000–2014, with a particular emphasis on metal-catalyzed methods.

Keywords: vinylsilanes • vinylmetals • transition-metal catalysis • hydrosilylation • alkynes • silylmetalation • alkynylsilanes • hydrogenation • hydrometalation • coupling reactions • dehydrogenative silylation • alkenes • carbometalation • metathesis • rearrangements

31.1.2 Fluoroarenes

A. Harsanyi and G. Sandford

This chapter is an update to the earlier Science of Synthesis contribution (Section 31.1) describing methods for the synthesis of fluoroarenes. It focuses on the literature published in the period 2007–2014, with a particular emphasis on transition-metal-mediated fluorination processes.

Keywords: organofluorine • fluoroarenes • fluoroaromatics • fluorination • transition-metal-mediated fluorination

31.2.3 Chloroarenes

S. P. Stanforth

This chapter updates the previous Science of Synthesis contribution (Section 31.2) published in 2007. Methods for the chlorination of arenes are described. The application of chloroarenes in synthesis, principally in transition-metal-catalyzed cross-coupling reactions, is discussed.

Keywords: chlorination • cross-coupling reactions • transition-metal-catalyzed reactions • aryl—carbon bond formation • aryl—heteroatom bond formation

31.3.3 Bromoarenes

S. P. Stanforth

This chapter updates the previous Science of Synthesis contribution (Section 31.3), published in 2007, describing the preparation of bromoarenes and their applications in synthesis. In recent years, the use of bromoarenes in transition-metal-catalyzed cross-coupling reactions has attracted considerable interest.

Keywords: bromoarenes • bromination • cross-coupling reactions • Suzuki reaction • Sonogashira reaction • Buchwald–Hartwig reaction • hydrodebromination • transhalogenation

31.4.1.3 Hypervalent Iodoarenes and Aryliodonium Salts

V. V. Zhdankin

This chapter provides an update to the earlier Science of Synthesis contribution (Section 31.4.1) describing the preparation and synthetic applications of hypervalent iodoarenes and aryliodonium salts. Recently, the chemistry of hypervalent iodine compounds has experienced several significant new developments, the most important of which are represented by the discovery of catalytic reactions promoted by in situ generated hypervalent iodine species, the development of highly enantioselective reactions of chiral hypervalent iodine reagents, and the preparation and synthetic application of numerous recyclable hypervalent iodine reagents.

Keywords: iodine • iodonium compounds • alkynylation • arylation • trifluoromethylation • oxidation • oxidative cleavage • catalysts • chiral compounds • fluorination • iodination • Hofmann rearrangement

31.41.3 Arylphosphine Oxides and Heteroatom Derivatives

O. M. Demchuk, M. Stankevič, and K. M. Pietrusiewicz

This chapter is an expanded update to the earlier Science of Synthesis contribution (Section 31.41), describing methods for the synthesis of arylphosphine oxides, arylphosphine sulfides, arylphosphine selenides, and aryl(imino)phosphoranes. Classical routes to arylphosphine chalcogenides involve the oxidation of parent phosphines by the pertinent chalcogenide oxidant. Other methods involve the formation of the lacking P—C bond(s) in oxidized electrophilic, nucleophilic, and radical phosphorus(V) precursors. Newer methods are based on hydrophosphinylation and coupling processes catalyzed by transition-metal complexes. Classical synthesis of aryl(imino)phosphoranes involves the reaction of the parent phosphines with organic azides (the Staudinger reaction), but methods based on the use of aminophosphonium intermediates are also reviewed. Approaches involving modifications of the carbon skeleton in existing arylphosphine chalcogenides are included as well.

Keywords: phosphorus compounds • phosphines • phosphine oxides • phosphine sulfides • phosphine selenides • iminophosphoranes • phosphorus heterocycles • phosphinylation • addition reactions • nucleophilic substitution • coupling reactions • cycloadditions • 1,3-dipolar cycloaddition • oxidation • radical addition • P—C bond formation • P—C bond cleavage

35.2.5.1.9 Synthesis by Addition across C=C Bonds

G. Dagousset and G. Masson

This chapter is an update to the earlier Science of Synthesis Section 35.2.5.1, written by Troll in 2006, on the synthesis of 1-bromo-n-heteroatom-functionalized alkanes (n ≥2), with both functions formed simultaneously by addition across C=C bonds. It focuses on recent advances in the field of bromofunctionalization of alkenes in the period 2007–2014, in particular on catalytic enantioselective syntheses.

Keywords: bromine compounds • carbon—bromine bonds • carbon—heteroatom bonds • bromination of alkenes • alkoxybromination of alkenes • bromolactonization • aminobromination • catalytic enantioselective reactions

Science of Synthesis Knowledge Updates 2015/1

Preface

Abstracts

Table of Contents

4.4.4.8 Silyl Hydrides (Update 2015)

R. W. Clark and S. L. Wiskur

4.4.34.35 Vinylsilanes (Update 2015)

E. A. Anderson and D. S. W. Lim

31.1.2 Fluoroarenes (Update 2015)

A. Harsanyi and G. Sandford

31.2.3 Chloroarenes (Update 2015)

S. P. Stanforth

31.3.3 Bromoarenes (Update 2015)

S. P. Stanforth

31.4.1.3 Hypervalent Iodoarenes and Aryliodonium Salts (Update 2015)

V. V. Zhdankin

31.41.3 Arylphosphine Oxides and Heteroatom Derivatives (Update 2015)

O. M. Demchuk, M. Stankevič, and K. M. Pietrusiewicz

35.2.5.1.9 Synthesis by Addition across C=C Bonds (Update 2015)

G. Dagousset and G. Masson

Author Index

Abbreviations

Table of Contents

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

4.4 Product Class 4: Silicon Compounds

4.4.4.8 Silyl Hydrides

R. W. Clark and S. L. Wiskur

4.4.4.8 Silyl Hydrides

4.4.4.8.1 Synthesis of Silyl Hydrides

4.4.4.8.1.1 Method 1: From Inorganic Silanes

4.4.4.8.1.2 Method 2: From Alkyl-orArylsilanes

4.4.4.8.1.3 Method 3: From Silyl Halides

4.4.4.8.1.4 Method 4: From Silyl Ethers

4.4.4.8.1.5 Method 5: From Other Silyl Hydrides by Monohalogenation or Deuterium Exchange

4.4.4.8.2 Applications of Silyl Hydrides in Organic Synthesis

4.4.4.8.2.1 Method 1: Hydrosilylation of Alkenes, Alkynes, and Related Compounds

4.4.4.8.2.2 Method 2: Silyl Hydrides as Reducing Agents

4.4.4.8.2.3 Method 3: Dehydrogenative Silylation

4.4.34.35 Vinylsilanes

E. A. Andersonand D. S. W. Lim

4.4.34.35 Vinylsilanes

4.4.34.35.1 Vinylmetal Addition to Silane Electrophiles

4.4.34.35.1.1 Method 1: Addition to Chlorosilanes

4.4.34.35.1.2 Method 2: Addition to Cyclic Siloxanes

4.4.34.35.2 Hydrosilylation of Alkynes

4.4.34.35.2.1 Method 1: Transition-Metal-Catalyzed β-Hydrosilylation of Terminal Alkynes To Give E-Vinylsilanes

4.4.34.35.2.1.1 Variation 1: PlatinumCatalysis

4.4.34.35.2.1.2 Variation 2: Rhodium Catalysis

4.4.34.35.2.1.3 Variation 3: PalladiumCatalysis

4.4.34.35.2.1.4 Variation 4: Iridium Catalysis

4.4.34.35.2.2 Method 2: Transition-Metal-Catalyzed β-Hydrosilylation of Terminal Alkynes To Give Z-Vinylsilanes

4.4.34.35.2.2.1 Variation 1: Ruthenium Catalysis

4.4.34.35.2.2.2 Variation 2: Rhodium Catalysis

4.4.34.35.2.2.3 Variation 3: Iridium Catalysis

4.4.34.35.2.3 Method 3: Transition-Metal-Catalyzed α-Hydrosilylation of Terminal Alkynes

4.4.34.35.2.3.1 Variation 1: Ruthenium Catalysis

4.4.34.35.2.3.2 Variation 2: PlatinumCatalysis

4.4.34.35.2.4 Method 4: Transition-Metal-Catalyzed syn Hydrosilylation of Internal Alkynes

4.4.34.35.2.4.1 Variation 1: Platinum Catalysis

4.4.34.35.2.4.2 Variation 2: PalladiumCatalysis

4.4.34.35.2.5 Method 5: Transition-Metal-Catalyzed anti Hydrosilylation of Internal Alkynes

4.4.34.35.2.6 Method 6: Lewis Acid CatalyzedHydrosilylation

4.4.34.35.2.7 Method 7: RadicalHydrosilylation

4.4.34.35.3 Silylmetalation of Alkynes

4.4.34.35.3.1 Method 1: Silylcupration

4.4.34.35.3.1.1 Variation 1: Silylcupration Using Silyllithium Reagents

4.4.34.35.3.1.2 Variation 2: Silylcupration Using Silylboronic EsterReagents

4.4.34.35.3.2 Method 2: Copper-Catalyzed Silylmetalation

4.4.34.35.3.3 Method 3: Silylzincation

4.4.34.35.3.4 Method 4: Silylrhodation

4.4.34.35.4 Addition to Alkynylsilanes

4.4.34.35.4.1 Method 1: Hydrogenation

4.4.34.35.4.2 Method 2: Hydrometalation

4.4.34.35.4.2.1 Variation 1: HydrometalationFollowed by Protodemetalation

4.4.34.35.4.2.2 Variation 2: HydrometalationFollowed by Halogenation

4.4.34.35.4.2.3 Variation 3: HydrometalationFollowed by Alkylation

4.4.34.35.4.3 Method 3: Carbometalation

4.4.34.35.5 Intermolecular Coupling of Alkynylsilanes

4.4.34.35.5.1 Method 1: Ruthenium-Catalyzed Alder-Ene Reaction

4.4.34.35.5.2 Method 2: Reductive Coupling

4.4.34.35.5.3 Method 3: Enyne Cross Metathesis

4.4.34.35.6 Ring-Closing Metathesis of α-Substituted Vinylsilanes

4.4.34.35.7 Dehydrogenative Silylation of Alkenes

4.4.34.35.7.1 Method 1: Reaction with Silanes

4.4.34.35.7.2 Method 2: Reaction with Halosilanes or Silyl Trifluoromethanesulfonates

4.4.34.35.7.3 Method 3: Transfer Silylation

4.4.34.35.7.4 Method 4: Reaction with Siletanes

4.4.34.35.8 Carbometalation of Vinylsilanes

4.4.34.35.8.1 Method 1: Heck Reaction with Aryl Halides

4.4.34.35.8.2 Method 2: Heck-Type Reaction with Benzonitriles

4.4.34.35.8.3 Method 3: Iron-Catalyzed Oxidative Arylation

4.4.34.35.9 Addition to Carbonyl Compounds

4.4.34.35.9.1 Method 1: Reaction with (Dihalomethyl)silane Reagents

4.4.34.35.9.2 Method 2: Reaction with Disilylmethyllithium Reagents

4.4.34.35.9.3 Method 3: Reaction with (Halomethyl)silane Reagents

4.4.34.35.9.4 Method 4: Reaction with (α-Silylallyl)borane Reagents

4.4.34.35.10 Rearrangements

4.4.34.35.10.1 Method 1: Gold-Catalyzed Rearrangement of Allyl(alkynyl)silanes

4.4.34.35.10.2 Method 2: Rearrangement of (α-Hydroxypropargyl)silanes

4.4.34.35.10.3 Method 3: Rearrangement of Silyl Allenoates

4.4.34.35.11 Synthesis of Cyclic Vinylsilanes

4.4.34.35.11.1 Method 1: Intramolecular Hydrosilylation of Alkynes

4.4.34.35.11.1.1 Variation 1: Metal-Catalyzed syn-exo Hydrosilylation

4.4.34.35.11.1.2 Variation 2: Metal-Catalyzed anti-exo Hydrosilylation

4.4.34.35.11.1.3 Variation 3: Metal-Catalyzed endo-Hydrosilylation

4.4.34.35.11.1.4 Variation 4: Base-Promoted Hydrosilylation

4.4.34.35.11.2 Method 2: Cyclization of Vinylsilanes

4.4.34.35.11.2.1 Variation 1: By Ring-Closing Metathesis with Terminal Vinylsilanes

4.4.34.35.11.2.2 Variation 2: By Silylvinylation

4.4.34.35.11.3 Method 3: Cyclization of Alkynylsilanes

4.4.34.35.11.3.1 Variation 1: By Ring-Closing Enyne Metathesis

4.4.34.35.11.3.2 Variation 2: By Reductive Coupling of Alkynylsilanes

4.4.34.35.11.3.3 Variation 3: By Gold-CatalyzedCyclization

4.4.34.35.11.3.4 Variation 4: By Semihydrogenation

4.4.34.35.11.4 Method 4: Three-ComponentCoupling

4.4.34.35.11.5 Method 5: Ring Contraction of Cyclic Vinylsilanes

4.4.34.35.12 Synthesis from Acylsilanes

4.4.34.35.13 Synthesis from Allenes

4.4.34.35.13.1 Method 1: Hydrosilylation

4.4.34.35.13.2 Method 2: Silylmetalation

31.1 Product Class 1: Fluoroarenes

31.1.2 Fluoroarenes

A. Harsanyi and G. Sandford

31.1.2 Fluoroarenes

31.1.2.1 Synthesis of Fluoroarenes

31.1.2.1.1 Synthesis by Substitution of Hydrogen

31.1.2.1.1.1 Method 1: Reaction with Hydrogen Fluoride–Pyridine Complex

31.1.2.1.1.2 Method 2: Reaction with Silver(II) Fluoride

31.1.2.1.1.3 Method 3: Reaction with Fluorinating Agents Mediated by Transition-Metal Catalysts

31.1.2.1.2 Synthesis by Substitution of Organometallic Groups

31.1.2.1.2.1 Method 1: Substitution of Boronic Acids and Esters

31.1.2.1.2.1.1 Variation 1: Reaction with Silver(I) Trifluoromethanesulfonate and Selectfluor

31.1.2.1.2.1.2 Variation 2: Reaction with AcetylHypofluorite

31.1.2.1.2.1.3 Variation 3: Palladium-Catalyzed Fluorodeboronation

31.1.2.1.2.1.4 Variation 4: Copper-Catalyzed Fluorodeboronation

31.1.2.1.3 Synthesis by Substitution of Halogens

31.1.2.1.3.1 Method 1: Reaction with Anhydrous Tetrabutylammonium Fluoride

31.1.2.1.3.2 Method 2: Reactions Catalyzed by Transition Metals

31.1.2.1.3.2.1 Variation 1: Palladium-Catalyzed Reactions

31.1.2.1.3.2.2 Variation 2: Copper-Catalyzed Reactions

31.1.2.1.4 Synthesis by Substitution of Nitrogen

31.1.2.1.5 Synthesis by Substitution of Oxygen

31.1.2.1.5.1 Method 1: Palladium-Catalyzed Displacement of Trifluoromethanesulfonate by Cesium Fluoride

31.1.2.1.5.2 Method 2: Deoxyfluorination Using PhenoFluor

31.2 Product Class 2: Chloroarenes

31.2.3 Chloroarenes

S. P. Stanforth

31.2.3 Chloroarenes

31.2.3.1 Synthesis of Chloroarenes

31.2.3.1.1 Synthesis by Substitution

31.2.3.1.1.1 Method 1: Electrophilic Chlorination

31.2.3.1.1.1.1 Variation 1: Of Phenols and Anisoles

31.2.3.1.1.1.2 Variation 2: Of Anilines, Acetanilides, and Related Compounds

31.2.3.1.1.1.3 Variation 3: Of Benzene and Alkylbenzene Derivatives

31.2.3.1.1.1.4 Variation 4: Of Electron-Deficient Benzene Derivatives

31.2.3.1.1.2 Method 2: Substitution of Boron

31.2.3.1.1.3 Method 3: Substitution of Bromine

31.2.3.1.2 Synthesis by Addition–Elimination

31.2.3.2 Applications of ChloroarenesinOrganic Synthesis

31.2.3.2.1 Method 1: Cross-Coupling Reactions

31.2.3.2.1.1 Variation 1: Synthesis of Biaryls

31.2.3.2.1.2 Variation 2: Synthesis of Arylalkenes

31.2.3.2.1.3 Variation 3: Synthesis of Arylalkynes

31.2.3.2.1.4 Variation 4: Synthesis of Arylalkanes

31.2.3.2.1.5 Variation 5: Carbonylation and Cyanation Reactions

31.2.3.2.1.6 Variation 6: Metal-CatalyzedHeterosubstitution Reactions

31.3 Product Class 3: Bromoarenes

31.3.3 Bromoarenes

S. P. Stanforth

31.3.3 Bromoarenes

31.3.3.1 Synthesis of Bromoarenes

31.3.3.1.1 Synthesis by Substitution

31.3.3.1.1.1 Method 1: Electrophilic Bromination

31.3.3.1.1.1.1 Variation 1: Of Phenols and Anisoles

31.3.3.1.1.1.2 Variation 2: Of Anilines, Acetanilides, and Related Compounds

31.3.3.1.1.1.3 Variation 3: Of Benzene and Alkylbenzene Derivatives

31.3.3.1.1.1.4 Variation 4: Of Electron-Deficient Benzene Derivatives

31.3.3.1.1.1.5 Variation 5: Of Arylboronates

31.3.3.1.1.2 Method 2: Synthesis from Organometallics

31.3.3.1.1.2.1 Variation 1: From Arylboronates

31.3.3.1.1.3 Method 3: Substitution of a Trifluoromethanesulfonate Group

31.3.3.2 Applications of Bromoarenes in Organic Synthesis

31.3.3.2.1 Method 1: Cross-Coupling Reactions

31.3.3.2.1.1 Variation 1: Synthesis of Biaryls

31.3.3.2.1.2 Variation 2: Synthesis of Arylalkenes

31.3.3.2.1.3 Variation 3: Synthesis of Arylalkynes

31.3.3.2.1.4 Variation 4: Synthesis of Arylalkanes

31.3.3.2.1.5 Variation 5: Carbonylation and Cyanation Reactions

31.3.3.2.1.6 Variation 6: Metal-CatalyzedHeterosubstitution Reactions

31.3.3.2.1.7 Variation 7: Borylation Reactions

31.3.3.2.1.8 Variation 8: Phosphonylation Reactions

31.3.3.2.1.9 Variation 9: Transhalogenation Reactions

31.3.3.2.2 Method 2: Hydrodebromination Reactions

31.4 Product Class 4: Aryl Iodine Compounds

31.4.1.3 Hypervalent Iodoarenes and Aryliodonium Salts

V. V. Zhdankin

31.4.1.3 Hypervalent Iodoarenes and Aryliodonium Salts

31.4.1.3.1 Synthesis of Hypervalent Iodoarenes and Aryliodonium Salts

31.4.1.3.1.1 Synthesis by Oxidative Addition to Iodoarenes

31.4.1.3.1.1.1 Method 1: Iodylarenes by Oxidation of Iodoarenes

31.4.1.3.1.1.1.1 Variation 1: Acyclic Iodylarenes

31.4.1.3.1.1.1.2 Variation 2: Cyclic Iodylarenes

31.4.1.3.1.1.1.3 Variation 3: Polymer-Supported Iodylarenes

31.4.1.3.1.1.2 Method2: (Difluoroiodo)arenes by Fluorination of Iodoarenes

31.4.1.3.1.1.2.1 Variation 1: (Difluoroiodo)arenes by One-Pot Synthesis from Arenes

31.4.1.3.1.1.3 Method 3: (Dichloroiodo)arenes by Chlorination of Iodoarenes

31.4.1.3.1.1.4 Method 4: [Bis(acyloxy)iodo]arenes by Oxidation of Iodoarenes in the Presence of aCarboxylic Acid

31.4.1.3.1.1.5 Method 5: Aryliodine(III) Sulfonates by Oxidation of Iodoarenes in the Presence of aSulfonic Acid

31.4.1.3.1.2 Synthesis by LigandExchange of Hypervalent Iodine Compounds

31.4.1.3.1.2.1 Method 1: 1-Oxo-1-(tosyloxy)-1H-1λ5-benzo[d][1,2]iodoxol-3-one from 2-Iodoxybenzoic Acid by Exchange with 4-Toluenesulfonic Acid

31.4.1.3.1.2.2 Method 2: [Bis(acyloxy)iodo]arenes from Other [Bis(acyloxy)iodo]arenes by Exchange with Carboxylic Acids

31.4.1.3.1.2.3 Method 3: Phenyliodine(III) Sulfate from (Diacetoxyiodo)benzene

31.4.1.3.1.2.4 Method 4: Iodosylarenes by Hydrolysis of [Bis(acyloxy)iodo]arenes

31.4.1.3.1.2.5 Method 5: Aryliodine(III) Amides from (Acyloxyiodo)arenes

31.4.1.3.1.2.6 Method 6: Alkynyl(aryl)iodonium Salts from Hypervalent Iodoarenes

31.4.1.3.1.2.6.1 Variation 1: Alkynyl(aryl)iodonium Tetrafluoroborates

31.4.1.3.1.2.6.2 Variation 2: Alkynyl(aryl)iodonium Trifluoroacetates

31.4.1.3.1.2.6.3 Variation 3: Alkynyl(aryl)iodonium Organosulfonates

31.4.1.3.1.2.6.4 Variation 4: 1-Alkynylbenziodoxoles

31.4.1.3.1.2.7 Method 7: Aryl- and Hetaryliodonium Salts from Hypervalent Iodoarenes

31.4.1.3.1.2.7.1 Variation 1: AryliodoniumTetrafluoroborates

31.4.1.3.1.2.7.2 Variation 2: Aryl- and Hetaryliodonium Sulfonates

31.4.1.3.1.2.7.3 Variation 3: Aryliodonium Halides

31.4.1.3.1.2.7.4 Variation 4: 1-Arylbenziodoxoles

31.4.1.3.1.2.8 Method 8: 1-(Trifluoromethyl)benziodoxoles by Trifluoromethylation of Other Benziodoxoles

31.4.1.3.1.2.9 Method 9: AryliodoniumYlides from (Diacetoxyiodo)arenes

31.4.1.3.1.2.10 Method 10: AryliodoniumImides from (Diacetoxyiodo)arenes

31.4.1.3.2 Applications of Hypervalent Iodoarenes and Aryliodonium Salts in Organic Synthesis

31.4.1.3.2.1 Preparation of Products with a New C—C Bond

31.4.1.3.2.1.1 Method 1: Alkynylation Using 1-Alkynylbenziodoxoles

31.4.1.3.2.1.2 Method 2: Arylation Using Diaryliodonium Salts

31.4.1.3.2.1.3 Method 3: Trifluoromethylation Using (Trifluoromethyl)benziodoxoles

31.4.1.3.2.1.4 Method 4: Reactions of Aryliodonium Ylides

31.4.1.3.2.2 Preparation of Products with a New C—F Bond

31.4.1.3.2.2.1 Method 1: α-Fluorination of Carbonyl Compounds

31.4.1.3.2.2.2 Method 2: Fluorination of Aromatic Compounds

31.4.1.3.2.3 Preparation of Products with a New C—Cl Bond

31.4.1.3.2.3.1 Method 1: Chlorination of Unsaturated Compounds

31.4.1.3.2.4 Preparation of Products with a New C—I Bond

31.4.1.3.2.4.1 Method 1: Oxidative Iodination Using Hypervalent Iodoarenes

31.4.1.3.2.5 Oxidations and Oxidative Rearrangements

31.4.1.3.2.5.1 Reactions with Iodine(V) Reagents

31.4.1.3.2.5.1.1 Method 1: Oxidations with Iodylarenes

31.4.1.3.2.5.1.2 Method 2: Iodine(V)-Catalyzed Oxidations

31.4.1.3.2.5.1.2.1 Variation 1: Catalytic Oxidation of Alcohols to Carbonyl Compounds

31.4.1.3.2.5.1.2.2 Variation 2: Catalytic Oxidation at the Benzylic Position

31.4.1.3.2.5.1.2.3 Variation 3: Catalytic Preparation of α,β-Unsaturated Carbonyl Compounds

31.4.1.3.2.5.2 Reactions with Iodine(III) Reagents

31.4.1.3.2.5.2.1 Method 1: 2,2,6,6-Tetramethylpiperidin-1-oxyl-Catalyzed Oxidation of Alcohols

31.4.1.3.2.5.2.2 Method 2: Diacetoxylation of Alkenes

31.4.1.3.2.5.2.3 Method 3: Oxidative Dearomatization of Phenols and Phenol Ethers

31.4.1.3.2.5.2.3.1 Variation 1: Oxidation of 4-SubstitutedPhenols

31.4.1.3.2.5.2.3.2 Variation 2: Oxidation of 2-SubstitutedPhenols

31.4.1.3.2.5.2.4 Method 4: Iodine(III)-Catalyzed Oxidations

31.4.1.3.2.5.2.4.1 Variation 1: Catalytic α-Functionalization of Carbonyl Compounds

31.4.1.3.2.5.2.4.2 Variation 2: Catalytic Lactonization Reactions

31.4.1.3.2.5.2.4.3 Variation 3: Catalytic Stereoselective Diacetoxylation of Alkenes

31.4.1.3.2.5.2.4.4 Variation 4: Catalytic Oxidative Cleavage of Alkenes and Alkynes

31.4.1.3.2.5.2.4.5 Variation 5: Catalytic Spirocyclization of Aromatic Substrates

31.4.1.3.2.6 Preparation of Products with a New C—N Bond

31.4.1.3.2.6.1 Method 1: Azidations with Iodine(III) Reagents

31.4.1.3.2.6.2 Method 2: Aminations with Iodine(III) Reagents

31.4.1.3.2.6.3 Method 3: Reactions of Aryliodonium Imides

31.4.1.3.2.6.3.1 Variation 1: C—H Amidation

31.4.1.3.2.6.3.2 Variation 2: Aziridination of Alkenes

31.4.1.3.2.7 Oxidations at Nitrogen

31.4.1.3.2.7.1 Method 1: Hypervalent Iodoarenes as Reagents for Hofmann Rearrangement

31.4.1.3.2.7.1.1 Variation 1: Hypervalent Iodine CatalyzedHofmann Rearrangement

31.4.1.3.2.7.2 Method 2: Hypervalent Iodoarenes as Reagents for Generation of Nitrile Oxides from Oximes

31.4.1.3.2.7.2.1 Variation 1: Synthesis of Dihydroisoxazoles via Hypervalent Iodine Catalyzed Generation of Nitrile Oxides

31.41 Product Class 41: Arylphosphine Oxides

31.41.3 Arylphosphine Oxides and Heteroatom Derivatives

O. M. Demchuk, M. Stankevič,and K. M. Pietrusiewicz

31.41.3 Arylphosphine Oxides and Heteroatom Derivatives

31.41.3.1 Arylphosphine Oxides

31.41.3.1.1 Synthesis of Arylphosphine Oxides

31.41.3.1.1.1 Method 1: Oxidation of Phosphines and Derivatives

31.41.3.1.1.1.1 Variation 1: Oxidation with Dioxygen or Air

31.41.3.1.1.1.2 Variation 2: Catalytic Oxidation

31.41.3.1.1.1.3 Variation 3: Oxidation with Peroxides

31.41.3.1.1.1.4 Variation 4: Photooxidation

31.41.3.1.1.1.5 Variation 5: Oxidation with Miscellaneous Oxidants

31.41.3.1.1.1.6 Variation 6: Oxidation of Chalcogen Phosphine Derivatives and Phosphine–Boranes

31.41.3.1.1.2 Method 2: Addition of Secondary Phosphine Oxides to Unsaturated Bonds

31.41.3.1.1.2.1 Variation 1: Addition to Unsaturated Carbon—Carbon Bonds

31.41.3.1.1.2.2 Variation 2: Addition to Imines

31.41.3.1.1.2.3 Variation 3: Addition to Carbonyl Compounds

31.41.3.1.1.2.4 Variation 4: Conjugate Addition to Activated Alkenes

31.41.3.1.1.3 Method 3: Nucleophilic Substitution at the Phosphorus Atom

31.41.3.1.1.3.2 Variation 2: P—O Bond Cleavage

31.41.3.1.1.3.3 Variation 3: P—C Bond Cleavage

31.41.3.1.1.3.4 Variation 4: Hydrolysis of Phosphonium Salts

31.41.3.1.1.3.5 Variation 5: Electrophilic Aromatic Substitution

31.41.3.1.1.4 Method 4: Nucleophilic Substitution with Phosphorus Nucleophiles

31.41.3.1.1.4.1 Variation 1: Michaelis–Becker Reactions

31.41.3.1.1.4.2 Variation 2: Michaelis–Arbuzov Reactions

31.41.3.1.1.5 Method 5: Transition-Metal-Mediated P—C Bond Formation

31.41.3.1.1.5.1 Variation 1: Copper-Mediated Reactions

31.41.3.1.1.5.2 Variation 2: Nickel-Mediated Reactions

31.41.3.1.1.5.3 Variation 3: Palladium-Mediated Reactions

31.41.3.1.1.5.4 Variation 4: Other Metal-Mediated Reactions

31.41.3.1.1.6 Method 6: Other Reactions

31.41.3.1.1.6.1 Variation 1: Phosphinylation of Ortho Esters

31.41.3.1.1.6.2 Variation 2: Manganese(III)-Mediated Free-Radical Phosphinylation

31.41.3.1.1.6.3 Variation 3: Palladium-Catalyzed Intramolecular Dehydrogenative Cyclization

31.41.3.1.1.6.4 Variation 4: Reaction of Elemental Phosphorus

31.41.3.1.1.6.5 Variation 5: The Wittig Reaction

31.41.3.1.1.6.6 Variation 6: The Appel Reaction

31.41.3.1.1.6.7 Variation 7: The Mitsunobu Reaction

31.41.3.1.1.7 Method 7: Modification of Phosphine Oxides without Substitution at Phosphorus

31.41.3.1.1.7.1 Variation 1: Monoreduction of Bisphosphine Dioxides

31.41.3.1.1.7.2 Variation 2: Deprotonation Directed by the P=OGroup

31.41.3.1.1.7.3 Variation 3: Nucleophilic Aromatic Substitution Promoted by the P=O Group

31.41.3.1.1.7.4 Variation 4: Alkene Metathesis

31.41.3.1.1.7.5 Variation 5: Cycloaddition Reactions

31.41.3.1.1.7.6 Variation 6: Annulation Reactions

31.41.3.1.1.7.7 Variation 7: Cross-Coupling Reactions

31.41.3.1.2 Applications of Arylphosphine Oxides in Organic Synthesis

31.41.3.2 Arylphosphine Sulfides

31.41.3.2.1 Synthesis of Arylphosphine Sulfides

31.41.3.2.1.1 Method 1: Sulfuration of Phosphines

31.41.3.2.1.1.1 Variation 1: Using Elemental Sulfur

31.41.3.2.1.1.2 Variation 2: Using Polysulfide Reagents

31.41.3.2.1.1.3 Variation 3: Using Other Sulfur Sources

31.41.3.2.1.1.4 Variation 4: Via Sulfuration of Phosphine–Borane Species

31.41.3.2.1.1.5 Variation 5: Via Sulfuration of Other Chalcogen Phosphine Derivatives

31.41.3.2.1.2 Method 2: Addition of Secondary Phosphine Sulfides to Unsaturated Bonds

31.41.3.2.1.2.1 Variation 1: Addition to Carbonyl Compounds

31.41.3.2.1.2.2 Variation 2: Addition to Alkenes

31.41.3.2.1.2.3 Variation 3: Conjugate Addition to Activated Alkenes

31.41.3.2.1.3 Method 3: Nucleophilic Substitution with Phosphorus Nucleophiles

31.41.3.2.1.3.1 Variation 1: Transition-Metal-Mediated Substitution

31.41.3.2.1.3.2 Variation 2: Thio-Michaelis–Arbuzov Reactions

31.41.3.2.1.4 Method 4: Nucleophilic Substitution at the Phosphorus Atom

31.41.3.2.1.4.2 Variation 2: P—S Bond Cleavage

31.41.3.2.1.4.3 Variation 3: P—C Bond Cleavage

31.41.3.2.1.4.4 Variation 4: P—O Bond Cleavage

31.41.3.2.1.4.5 Variation 5: Solvolysis of Phosphorus(V) Compounds

31.41.3.2.1.5 Method 5: Other Reactions

31.41.3.2.1.5.1 Variation 1: Reaction of Sulfides with Elemental Phosphorus

31.41.3.2.1.5.2 Variation 2: Cycloaddition of Strained Cyclic Phosphine Sulfides with Dienes

31.41.3.2.1.5.3 Variation 3: Wittig Reaction with Thiocarbonyl Compounds

31.41.3.2.1.5.4 Variation 4: Reaction of Ylides with Elemental Sulfur and with Thiiranes

31.41.3.2.1.5.5 Variation 5: Cycloaddition of (Alkylsulfanyl)(chloro)phosphines

31.41.3.2.1.5.6 Variation 6: Reaction of Butadienylphosphine Sulfides

31.41.3.2.1.6 Method 6: Modification of Phosphine Sulfides without Substitution at Phosphorus

31.41.3.2.1.6.1 Variation 1: α-and ortho-Deprotonation

31.41.3.2.1.6.2 Variation 2: Cycloaddition Reactions

31.41.3.2.1.6.3 Variation 3: Annulation Reactions

31.41.3.2.2 Applications of Arylphosphine Sulfides in Organic Synthesis

31.41.3.3 Arylphosphine Selenides

31.41.3.3.1 Synthesis of Arylphosphine Selenides

31.41.3.3.1.1 Method 1: Selenation of Free Phosphines with Elemental Selenium

31.41.3.3.1.2 Method 2: Other Methods

31.41.3.3.2 Applications of Arylphosphine Selenides in Organic Synthesis

31.41.3.4 Aryl(imino)phosphoranes

31.41.3.4.1 Synthesis of Aryl(imino)phosphoranes

31.41.3.4.1.1 Method 1: The Staudinger Reaction of Free Phosphines and Azides

31.41.3.4.1.2 Method 2: Synthesis via Aminophosphonium Salts

31.41.3.4.2 Applications of Aryl(imino)phosphoranes in Organic Synthesis

Volume 35: Chlorine,Bromine,and Iodine

35.2 Product Class 2: One SaturatedCarbon—Bromine Bond

35.2.5.1.9 Synthesis by Addition across C=C Bonds

G. Dagousset and G. Masson

35.2.5.1.9 Synthesis by Addition across C=C Bonds

35.2.5.1.9.1 Method 1: Hydroxy- and Alkoxybromination of Alkenes

35.2.5.1.9.2 Method 2: Aminobromination of Alkenes

35.2.5.1.9.3 Method 3: Azidobromination of Alkenes

35.2.5.1.9.4 Method 4: Phosphobromination of Alkenes

35.2.5.1.9.5 Method 5: Catalytic Enantioselective Syntheses

35.2.5.1.9.5.1 Variation 1: Bromination of Alkenes

35.2.5.1.9.5.2 Variation 2: Hydroxy- and Alkoxybromination of Alkenes

35.2.5.1.9.5.3 Variation 3: Aminobromination of Alkenes

Author Index

Abbreviations

4.4.4.8 Silyl Hydrides (Update 2015)

R. W. Clark and S. L. Wiskur

General Introduction

The product subclass discussed herein is previously discussed in Houben–Weyl, Vol. 13/5, pp 79–96; silyl hydrides and their application as reducing agents is included in Houben–Weyl, Vol. 13/5, pp 350–360. More detailed examples include asymmetric reductions (Houben–Weyl, Vol. E 21, pp 4067–4081), transition-metal-catalyzed hydrosilylations (Houben–Weyl, Vol. E 18, pp 685–742), and stereoselective hydrosilylations of alkenes and dienes (Houben–Weyl, Vol. E 21, pp 5733–5740). This section is limited in scope to silicon-based compounds containing at least one Si-H bond. Specifically, the subsequent section highlights recent scientific discoveries regarding the subclass since last reviewed in in 2001 (Section 4.4.4). The text that follows is not all inclusive, but rather seeks to highlight the most synthetically viable preparation methods for this class of compounds, including the preparation of chlorinated silyl hydrides and silyl hydrides that are stereogenic at silicon. The use of these silyl hydrides will also be explored. The application of silyl hydrides as reagents in other important synthetic processes is of particular interest; therefore, this update has a large focus on this. Progress in the field of hydrosilylation, reduction, and dehydrogenative silylation of carbonyl compounds, alkenes, alkynes, and other functional groups is discussed in the following sections.