Practical Functional Group Synthesis, Enhanced E-Book E-Book

Robert A. Stockland

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Veröffentlichungsjahr: 2016

Beschreibung

A practical handbook for chemists performing bond forming reactions, this book features useful information on the synthesis of common functional groups in organic chemistry.

• Details modern functional group synthesis through carbon-heteroelement (N, O, P, S, B, halogen) bond forming reactions with a focus on operational simplicity and sustainability.
• Summarizes key and recent developments – which are otherwise scattered across journal literature – into a single source
• Contains over 100 detailed preparations of common functional groups
• Included 25 troubleshooting guides with suggestions and potential solutions to common problems.
• Complements the text in enhanced ebook editions with tutorial videos where the author provides an introduction to microwave assisted chemistry

Leseprobe

Table of Contents

COVER

TITLE PAGE

PREFACE

ACKNOWLEDGMENTS

1 INTRODUCTION TO PRACTICAL FUNCTIONAL GROUP SYNTHESIS

1.1 GENERAL APPROACHES FOR DESIGNING SYNTHESES

1.2 NEW VERSIONS OF “CLASSIC” ORGANIC REACTIONS

1.3 SOLVENT SELECTION AND SOLVENT-FREE REACTIONS

1.4 OPERATIONAL SIMPLICITY

1.5 METAL-CATALYZED TRANSFORMATIONS

1.6 ORGANOCATALYSIS

1.7 MICROWAVE- AND ULTRASOUND-ASSISTED CHEMISTRY

1.8 SUSTAINABILITY

1.9 ASYMMETRIC SYNTHESIS

REFERENCES

2 PREPARATION OF ALCOHOLS, ETHERS, AND RELATED COMPOUNDS

2.1 PREPARATION OF ALCOHOLS, ETHERS, AND RELATED COMPOUNDS THROUGH THE FORMATION OF OXYGEN–CARBON(

SP

3

) BONDS

2.2 PREPARATION OF PHENOLS, ARYL ETHERS, AND RELATED COMPOUNDS THROUGH THE FORMATION OF OXYGEN–CARBON(

SP

2

) BONDS

2.3 PREPARATION OF VINYL ETHERS AND RELATED COMPOUNDS THROUGH THE FORMATION OF OXYGEN–CARBON(

SP

2

) BONDS

2.4 PREPARATION OF ALKYNYL ETHERS AND RELATED COMPOUNDS THROUGH THE FORMATION OF OXYGEN–CARBON(

SP

) BONDS

REFERENCES

3 SYNTHESIS OF AMINES, AMIDES, AND RELATED COMPOUNDS

ALKYLAMINES

3.1 SYNTHESIS OF ALKYLAMINES AND RELATED COMPOUNDS THROUGH NITROGEN–CARBON(

SP

3

) BOND-FORMING REACTIONS

3.2 SYNTHESIS OF ARYLAMINES AND RELATED COMPOUNDS THROUGH NITROGEN–CARBON(

SP

2

) BOND-FORMING REACTIONS

3.3 SYNTHESIS OF VINYLAMINES AND RELATED COMPOUNDS THROUGH NITROGEN–CARBON(

SP

2

) BOND-FORMING REACTIONS

3.4 SYNTHESIS OF YNAMIDES AND RELATED COMPOUNDS THROUGH NITROGEN–CARBON(

SP

) BOND-FORMING REACTIONS

REFERENCES

4 SYNTHESIS OF ORGANOPHOSPHINES, PHOSPHONATES, AND RELATED COMPOUNDS

4.1 INTRODUCTION TO THE SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS GENERATED THROUGH THE FORMATION OF PHOSPHORUS–CARBON BONDS

4.2 SYNTHESIS OF ALKYLPHOSPHINES AND RELATED COMPOUNDS THROUGH THE FORMATION OF PHOSPHORUS–CARBON(

SP

3

) BONDS

4.3 SYNTHESIS OF ARYLPHOSPHINES AND RELATED COMPOUNDS THROUGH THE FORMATION OF PHOSPHORUS–CARBON(

SP

2

) BONDS

4.4 SYNTHESIS OF VINYLPHOSPHINES AND RELATED COMPOUNDS THROUGH THE FORMATION OF PHOSPHORUS–CARBON(

SP

2

) BONDS

4.5 SYNTHESIS OF ALKYNYLPHOSPHINES AND RELATED COMPOUNDS THROUGH THE FORMATION OF PHOSPHORUS–CARBON(

SP

) BONDS

REFERENCES

5 SYNTHESIS OF THIOETHERS, SULFONES, AND RELATED COMPOUNDS

5.1 SYNTHESIS OF THIOETHERS AND RELATED COMPOUNDS THROUGH THE FORMATION OF SULFUR–CARBON(

SP

3

) BONDS

5.2 SYNTHESIS OF ARYL THIOETHERS AND RELATED COMPOUNDS THROUGH THE FORMATION OF SULFUR–CARBON(

SP

2

) BONDS

5.3 SYNTHESIS OF VINYL THIOETHERS AND RELATED COMPOUNDS THROUGH THE FORMATION OF SULFUR–CARBON(

SP

2

) BONDS

5.4 SYNTHESIS OF THIOETHERS AND RELATED COMPOUNDS THROUGH THE FORMATION OF SULFUR–CARBON(

SP

) BONDS

REFERENCES

6 SYNTHESIS OF ORGANOBORONIC ACIDS, ORGANOBORONATES, AND RELATED COMPOUNDS

6.1 SYNTHESIS OF ALKYLBORONATES AND RELATED COMPOUNDS THROUGH THE FORMATION OF BORON–CARBON(SP

3

) BONDS

6.2 SYNTHESIS OF ARYLBORONATES AND RELATED COMPOUNDS THROUGH THE FORMATION OF BORON–CARBON(SP

2

) BONDS

6.3 SYNTHESIS OF VINYLBORONATES AND RELATED COMPOUNDS THROUGH THE FORMATION OF BORON–CARBON(

SP

2

) BONDS

6.4 SYNTHESIS OF ALKYNYLBORONATES AND RELATED COMPOUNDS THROUGH THE FORMATION OF BORON–CARBON(

SP

) BONDS

REFERENCES

7 SYNTHESIS OF ORGANOHALIDES

7.1 SYNTHESIS OF ALKYL HALIDES THROUGH THE FORMATION OF HALOGEN–CARBON(

SP

3

) BONDS

7.2 SYNTHESIS OF ARYL HALIDES THROUGH THE FORMATION OF HALOGEN–CARBON(

SP

2

) BONDS

7.3 SYNTHESIS OF VINYL HALIDES THROUGH THE FORMATION OF HALOGEN–CARBON(

SP

2

) BONDS

7.4 SYNTHESIS OF ALKYNYL HALIDES THROUGH THE FORMATION OF HALOGEN–CARBON(

SP

) BONDS

REFERENCES

INDEX

END USER LICENSE AGREEMENT

List of Tables

Chapter 01

Table 1.1 Effect of Microwave Power on the Product Distribution of a

Phospha

-Michael Addition [52].

List of Illustrations

Chapter 01

SCHEME 1.1 Synthesis of alkyl aryl ethers using the cuprous iodide/phen catalyst system [5].

SCHEME 1.2 Synthesis of diaryl ethers using a discrete copper complex [6].

SCHEME 1.3 Synthesis of alkyl aryl ethers using aryltrifluoroborate salts [7].

SCHEME 1.4 Effect of solvent on the double hydrophosphination of alkynes [9].

FIGURE 1.1 Solvent-free reaction using both a solid and a liquid reagent.

FIGURE 1.2 Stability of common trialkylphosphines and dialkylbiarylphosphines.

SCHEME 1.5 Example of a rhodium-catalyzed carbon–oxygen bond-forming reaction [17].

SCHEME 1.6 Example of an asymmetric palladium-catalyzed carbon–nitrogen bond-forming reaction [18].

SCHEME 1.7 Example of a palladium-catalyzed carbon–phosphorus bond-forming reaction [19].

SCHEME 1.8 Example of a decarboxylative copper-promoted carbon–phosphorus bond-forming reaction [20].

SCHEME 1.9 Examples of a palladium-catalyzed carbon–fluorine bond-forming reaction [21].

SCHEME 1.10 Organocatalytic asymmetric synthesis of functionalized tetrahydrothiophenes [35].

SCHEME 1.11 Organocatalytic asymmetric synthesis of chromane derivatives [36].

SCHEME 1.12 Microwave-assisted aqueous alkylation of amines using an open vessel [47].

FIGURE 1.3 General relationship between the polarity of the solvent and the ability of the solvent to absorb microwave energy.

FIGURE 1.4 Example of a commercial microwave reactor with an integrated camera.

FIGURE 1.5 Before and after pictures of the reaction mixture. It should be noted that the picture of the final product has a slight yellow tint to the solution that is not shown in the B&W photo.

FIGURE 1.6 Pictures from inside the microwave cavity before, during, and following irradiation. It should be noted that the color of the reaction mixture is slightly yellow after a few minutes of irradiation. The color is not illustrated in this B&W photo. The bright spot in the middle of the frame is due to the LED light used to provide light in the otherwise dark cavity of the microwave reactor.

FIGURE 1.7 Stirring options when using small reactor vials.

FIGURE 1.8 Development of new approaches versus protection/deprotection strategies.

SCHEME 1.13 Lewis acid-catalyzed sequential synthesis of a pyridine [75].

SCHEME 1.14 One-pot sequential gold- and palladium-catalyzed reactions [76].

SCHEME 1.15 Amide synthesis at 25 °C using a continuous flow reactor [85].

SCHEME 1.16 Benzimidazole synthesis through microwave-assisted flow chemistry [86].

SCHEME 1.17 Methoxylation reactions using flow electrochemistry [89].

SCHEME 1.18 Microwave-assisted flow chemistry using ultralow catalyst loading [90].

SCHEME 1.19 Metal-free synthesis of a tetrazine using S

N

Ar chemistry [91].

SCHEME 1.20 Metal-free C–H azidation of electron-rich arenes [93].

SCHEME 1.21 C–H oxidative amination reaction [94].

Chapter 02

SCHEME 2.1 Ruthenium-catalyzed preparation of primary alcohols from alkynes [2].

SCHEME 2.2 Conversion of alkyltrifluoroborates into alcohols [3].

SCHEME 2.3 Synthesis of

Z

-allylic alcohols from conjugated dienes [4].

SCHEME 2.4 Preparation of alcohols from alkyl halides in ionic liquids [5].

SCHEME 2.5 Ruthenium-catalyzed CH hydroxylation of tertiary CH bonds [6].

SCHEME 2.6 Ruthenium-catalyzed CH hydroxylation using a discrete ruthenium catalyst [7].

SCHEME 2.7 Gold-catalyzed synthesis of alcohols through a three-component coupling reaction [8].

SCHEME 2.8 Metal-free CH hydroxylation of tertiary alkanes [9].

SCHEME 2.9 Asymmetric hydroxylation of enals catalyzed by an organocatalyst [11].

SCHEME 2.10 Asymmetric synthesis of allylic alcohols using an iridium-catalyzed process [13].

SCHEME 2.11 Preparation of photoactivatable fluorescein derivatives [15].

SCHEME 2.12 Ribofuranosylation of alcohols using ribofuranosyl iodides as substrates [17].

SCHEME 2.13 Ether synthesis through ruthenium catalyzed dehydrative etherification [18].

SCHEME 2.14 Copper-catalyzed oxa-Michael additions to acrylamide derivatives [20].

SCHEME 2.15 Gold-catalyzed addition of phenols to unactivated alkenes [22].

SCHEME 2.16 Triflic acid-promoted addition of phenols to unactivated alkenes [23].

SCHEME 2.17 Iodine-catalyzed synthesis of esters [24].

SCHEME 2.18 Gold-catalyzed synthesis of ethers through a three-component coupling reaction [8].

SCHEME 2.19 Preparation of esters through the gold-catalyzed addition of carboxylic acids to alkenes [22].

SCHEME 2.20 Ruthenium-catalyzed addition of carboxylic acids to alkenes [25].

SCHEME 2.21 Asymmetric bromoesterification of alkenes [26].

SCHEME 2.22 Enantioselective synthesis of functionalized chromanes [27].

SCHEME 2.23 Asymmetric synthesis of chromane derivatives using a proline derivative as an organocatalyst [28].

SCHEME 2.24 Preparation of oxetanes through a rhodium-catalyzed process [29].

SCHEME 2.25 Conversion of a diol into a carbonate using carbon dioxide [30].

SCHEME 2.26 Synthesis of cyclic carbonates using a porphyrin based catalyst [31].

SCHEME 2.27 Asymmetric epoxidation of chalcones using a Yb-based catalyst [35].

SCHEME 2.28 Synthesis of resolved steroidal epoxides through an aqueous Darzens-type reaction [36].

SCHEME 2.29 Iodinative cyclization of phosphoramidates [37].

SCHEME 2.30 Oxidation of aryltrifluoroborate salts using Oxone [3].

SCHEME 2.31

N

-oxide promoted conversion of arylboronic acids into phenols [41].

SCHEME 2.32 Conversion of arylboronic acids into phenols using visible light catalysis [42].

SCHEME 2.33 Conversion of arylhydrosilanes into phenols through a fluorine-free procedure [43].

SCHEME 2.34 Synthesis of phenols in water and air with copper(II) sulfate [44].

SCHEME 2.35 Use of copper oxide in the synthesis of phenols [45].

SCHEME 2.36 Copper-catalyzed coupling of aryl bromides/iodides with CsOH [46].

SCHEME 2.37 Synthesis of a bulky phenol through a copper-catalyzed coupling reaction [47].

SCHEME 2.38 Palladium-catalyzed synthesis of phenols from aryl chlorides [52].

SCHEME 2.39 Microwave-assisted conversion of vinyl bromides into alcohols [53].

SCHEME 2.40 Imidazole-functionalized phosphines as supporting ligands in phenol synthesis [55].

SCHEME 2.41 Tandem iridium-catalyzed CH borylation and oxidation for the synthesis of phenols [56].

SCHEME 2.42 Ruthenium-catalyzed ortho selective CH hydroxylation of arenes [57].

SCHEME 2.43 CH hydroxylation of arenes using ruthenium catalysts [58].

SCHEME 2.44 Synthesis of phenols using ruthenium/Selectfluor combinations [60].

SCHEME 2.45 Ruthenium-catalyzed hydroxylation of benzamides [61].

SCHEME 2.46 Synthesis of

ortho

-acylphenols [62].

SCHEME 2.47 Palladium-catalyzed CH hydroxylation using molecular oxygen [64].

SCHEME 2.48 Copper-promoted CH hydroxylation [65].

SCHEME 2.49 Palladium-catalyzed CH hydroxylation of 2-arylpyridines [66].

SCHEME 2.50 Benzoyl peroxide-promoted CH hydroxylation [67].

SCHEME 2.51 A-ring functionalization using copper catalysis [76].

SCHEME 2.52 Copper-catalyzed coupling of aryltrifluoroborates with protected serine [77].

SCHEME 2.53 Microwave-assisted synthesis of alkyl aryl ethers [78].

SCHEME 2.54 Chemoselective copper-catalyzed formation of alkyl aryl ethers [79].

SCHEME 2.55 Decarboxylative etherification of carboxylate salts [80].

SCHEME 2.56 Copper-catalyzed dehydrogenative alkoxylation of 2-arylpyridines [82].

SCHEME 2.57 Palladium-catalyzed preparation of alkyl aryl ethers [86].

SCHEME 2.58 Synthesis of alkyl aryl ethers using a dppf-supported palladium catalyst [85].

SCHEME 2.59 Palladium-catalyzed double pivaloxylation of arenes [88].

SCHEME 2.60 Copper-catalyzed coupling between phenols and arylboronic acids [71].

SCHEME 2.61 Intramolecular oxygen–carbon(sp

2

) bond formation through cross-coupling [90].

SCHEME 2.62 Copper-catalyzed synthesis of diaryl ethers through cross-coupling [74].

SCHEME 2.63 Copper-catalyzed coupling of iodonium salts with phenols [91].

SCHEME 2.64 Synthesis of diaryl ethers using a well-defined copper complex [92].

SCHEME 2.65 Synthesis of benzoxazoles through an organocatalytic approach [93].

SCHEME 2.66 Palladium-catalyzed synthesis of benzofuranones [94].

SCHEME 2.67 Synthesis of macrocycles through a series of S

N

Ar reactions [95].

SCHEME 2.68 Preparation of a crowded ether [96].

SCHEME 2.69 Synthesis of a crowded ether [96].

SCHEME 2.70 Palladium-catalyzed synthesis of heterocycles through CH activation [97].

SCHEME 2.71 Preparation of 2,5-disubstituted furans [98].

SCHEME 2.72 Copper-catalyzed cross-coupling between arylboronic acids and carboxylic acids [99].

SCHEME 2.73 Palladium-catalyzed copper-promoted oxidative carbonylation [97].

SCHEME 2.74 Iridium-catalyzed synthesis of vinyl ethers from vinyl acetate [102].

SCHEME 2.75 Synthesis of vinyl ethers through palladium-mediated transetherification [104].

SCHEME 2.76 Copper-catalyzed coupling of vinyl iodides with alcohols in air [105].

SCHEME 2.77 Copper-catalyzed coupling of vinylboronic acids with a phenol [107].

SCHEME 2.78 Copper-catalyzed synthesis of alkyl aryl ethers [108].

SCHEME 2.79 Copper-catalyzed coupling of vinylboronates with allylic alcohols [109].

SCHEME 2.80 Synthesis of crowded vinyl ethers using copper/nickel compounds [110].

SCHEME 2.81 Gold-catalyzed synthesis of vinyl ethers [114].

SCHEME 2.82 Gold-catalyzed synthesis of vinyl ethers using microwave heating [119].

SCHEME 2.83 Ruthenium-catalyzed synthesis of 1,3-dienyl ethers [98].

SCHEME 2.84 Copper-catalyzed intramolecular cyclization of alkynyl alcohols [124].

SCHEME 2.85 Gold-catalyzed intramolecular hydroalkoxylation of internal alkynes [125].

SCHEME 2.86 Synthesis of five-membered heterocycles by formally trapping cyclohexyne with a nitrone [126].

SCHEME 2.87 Synthesis of arylisochromenes through a hydroarylation/cycloisomerization reaction [127].

SCHEME 2.88 Synthesis of furan derivatives through an iron-catalyzed vinylogous iso-Nazarov reaction [128].

SCHEME 2.89 Synthesis of oxazoles through a two-step one-pot iodocyclization/oxidation process [129].

SCHEME 2.90 Copper-catalyzed cross-coupling of vinylboronic acids with carboxylic acids [99].

SCHEME 2.91 Markovnikov addition of carboxylic acids to alkynes [136].

SCHEME 2.92 Ruthenium-catalyzed anti-Markovnikov addition of carboxylic acids to alkynes [136].

SCHEME 2.93 Gold-catalyzed addition of carboxylic acids to alkynes [138].

SCHEME 2.94 Palladium-catalyzed addition of carboxylic acids to ynamides [139].

SCHEME 2.95 Silver-catalyzed addition of carboxylic acids to ynol ethers [140].

SCHEME 2.96 Rhodium-catalyzed anti-Markovnikov addition of carboxylic acids to alkynes [141].

SCHEME 2.97 Ruthenium-catalyzed synthesis of vinyl esters in water [142].

SCHEME 2.98 Ruthenium-catalyzed synthesis of dienyl acetates [143].

SCHEME 2.99 Silver-promoted cyclization to generate vinyl esters [144].

SCHEME 2.100 Gold-catalyzed synthesis of enol lactones using eutectic mixtures [145].

SCHEME 2.101 Cyclization of alkynoic acids using palladium pincer compounds to generate lactones [146, 147].

SCHEME 2.102 Synthesis of oxazepanones through a gold-catalyzed cyclization reaction [148].

SCHEME 2.103 Preparation of isocoumarins through a copper-catalyzed coupling reaction [149].

SCHEME 2.104 Synthesis of bicyclic heterocycles through a phosphine-catalyzed annulation reaction [151].

SCHEME 2.105 Gold-catalyzed synthesis of enol lactones through cycloisomerization [152].

SCHEME 2.106 Copper-catalyzed asymmetric synthesis of functionalized 2,3-dyhydropyrans [153].

SCHEME 2.107 Palladium-catalyzed intramolecular CH olefination [154].

SCHEME 2.108 Rhodium-catalyzed synthesis of

Z

-vinyl acetates from enamides [155].

SCHEME 2.109 Copper-catalyzed synthesis of alkoxyamines [156].

SCHEME 2.110 Ruthenium-catalyzed synthesis of phosphaisocoumarins [157].

SCHEME 2.111 Gold-catalyzed addition of sulfonic acids to alkynes [160].

SCHEME 2.112 Wacker oxidation of alkenes using oxygen as the oxidant [167].

SCHEME 2.113 An anti-Markovnikov selective Wacker-type oxidation [169].

SCHEME 2.114 Gold-catalyzed Markovnikov hydration of alkynes using low catalyst loading [175].

SCHEME 2.115 Ruthenium-catalyzed anti-Markovnikov hydration of alkynes [180].

SCHEME 2.116 Conversion of alkynones into diketones [181].

SCHEME 2.117 Ozonation of methylenecyclopropanes [182].

SCHEME 2.118 Oxidation of glycine derivatives by molecular oxygen [183].

SCHEME 2.119 Conversion of internal alkynes into maleic anhydrides [184].

SCHEME 2.120 Direct oxidation of CH bonds using an iron catalyst [185].

SCHEME 2.121 Synthesis of ynol ethers using an elimination approach [188].

SCHEME 2.122 Synthesis of a siloxy alkyne starting from a terminal acetylene [191].

SCHEME 2.123 Copper-promoted synthesis of ynol ethers [193].

SCHEME 2.124 Synthesis of ynol ethers from sulfonamides [195].

Chapter 03

SCHEME 3.1 Classic synthesis of nitrogen–carbon(sp

3

) bonds through substitution chemistry [1].

SCHEME 3.2 Microwave-assisted alkylation of benzylamine in an open flask [2].

SCHEME 3.3 Selective monoalkylation of aniline derivatives using alcohols and a ruthenium catalyst [3].

SCHEME 3.4 Iridium-catalyzed N-alkylation using alcohols [4].

SCHEME 3.5 Iridium-catalyzed N-alkylation using trialkylamines [4].

SCHEME 3.6 Rhenium-catalyzed alkylation of hydroxycarbamates [5].

SCHEME 3.7 Alkylation of aniline derivatives using carboxylic acids [6].

SCHEME 3.8 Preparation of amides through a copper-catalyzed photoinduced reaction [7].

SCHEME 3.9 Amine synthesis from alkylboronates [8].

SCHEME 3.10 Rhodium-catalyzed synthesis of cyclic sulfonamides [9].

SCHEME 3.11 Cobalt-catalyzed synthesis of nitrogen heterocycles under air [10].

SCHEME 3.12 Synthesis of heterocycles through oxidative amination chemistry [12].

SCHEME 3.13 Preparation of tetrahydropyrroles through bromocyclization [13].

SCHEME 3.14 Preparation of 1,2-dihydroquinolines through a bicyclization process [14].

SCHEME 3.15 Preparation of β-lactams and pyrrolidine-2,5-dione derivatives through multicomponent reactions [15].

SCHEME 3.16 Rhodium-catalyzed reactions of pyridotriazoles with amines and amides [16].

SCHEME 3.17 Stereoselective synthesis of propargylamines [17].

SCHEME 3.18 Silver-catalyzed synthesis of propargylamines through a multicomponent reaction [18].

SCHEME 3.19 Copper-catalyzed anti-Markovnikov hydroamination of alkenes [20].

SCHEME 3.20 Iron-catalyzed Markovnikov hydroamination of styrenes [21].

SCHEME 3.21 Copper-catalyzed preparation of cyclopropylaminoboronic esters [22].

SCHEME 3.22 Markovnikov addition of indoles to unactivated aliphatic alkenes [23].

SCHEME 3.23 Rhodium-catalyzed intramolecular cyclization to generate dihydroazepine derivatives [24].

SCHEME 3.24 Microwave-assisted synthesis of dihydroazepine derivatives [24].

SCHEME 3.25 Intramolecular alkene hydroamination using photoredox catalysis [25].

SCHEME 3.26 Silver-promoted synthesis of fused indolines [26].

SCHEME 3.27 Gadolinium-promoted synthesis of fused tetrahydroquinoline derivatives [26].

SCHEME 3.28 Ruthenium-catalyzed synthesis of functionalized dihydronaphthalenes and indenes [27].

SCHEME 3.29 Ruthenium-catalyzed formal N-methylation of imines [28].

SCHEME 3.30 Amine synthesis through a multicomponent coupling reaction [28].

SCHEME 3.31 Asymmetric synthesis of piperidines using phosphoric acid catalysts [29].

SCHEME 3.32 Synthesis of macrocyclic lactams through intramolecular cyclizations [30].

SCHEME 3.33 Enantioselective synthesis of pyrrolidines [31].

SCHEME 3.34 Copper-catalyzed preparation of chiral isoindolinones [32].

SCHEME 3.35 Highly regioselective aminofluorination of styrene [33].

SCHEME 3.36 Metal-free amination reaction using chiral phosphonium salts [34].

SCHEME 3.37 Asymmetric synthesis of pyrrolidinone and dihydropyridinones [35].

SCHEME 3.38 Synthesis of carbazoles through intramolecular oxidative C‒H amination [36].

SCHEME 3.39 Synthesis of

N

-arylindoles through a palladium-catalyzed annulation process [37].

SCHEME 3.40 Synthesis of amides from carboxylic acids through decarboxylative amidation [38].

SCHEME 3.41 Enantioselective synthesis of allylic amines [39].

SCHEME 3.42 Synthesis of

N,N

-bicyclic pyrazolidin-3-one derivatives [40].

SCHEME 3.43 Palladium-catalyzed aminocarbonylation using low-pressure CO (1 atm) [41].

SCHEME 3.44 Palladium-catalyzed synthesis of aniline derivatives [42].

SCHEME 3.45 Aniline synthesis through copper-promoted C‒H amination [43].

SCHEME 3.46 C‒H amidation of xanthones using sulfonyl azides [44].

SCHEME 3.47 C‒H amidation of 2-phenylpyridine [45].

SCHEME 3.48 Using BrettPhos as the supporting ligand in the coupling of aryl chlorides with primary amines [49].

SCHEME 3.49 Using RuPhos as the supporting ligand in the palladium-catalyzed coupling of aryl iodides with secondary amines [50].

SCHEME 3.50 Copper-catalyzed coupling of pyrimidines with arylboronic acids [51].

SCHEME 3.51 Using copper catalysts to generate arylamines [57].

SCHEME 3.52 Synthesis of arylamines using a discrete copper complex [58].

SCHEME 3.53 Copper-catalyzed coupling of arylboronic acids with chloroamides [59].

SCHEME 3.54 Synthesis of pyrroles through an iron-mediated domino reaction [60].

SCHEME 3.55 Palladium-catalyzed synthesis of pyrroles using molecular oxygen [61].

SCHEME 3.56 Synthesis of functionalized 2-aminoimidazoles through carboamination [62].

SCHEME 3.57 Gold-catalyzed synthesis of pyrroles from terminal alkynes [63].

SCHEME 3.58 Preparation of 1-amino-isoquinoline-

N

-oxides from 2-alkynylbenzaldoximes [64].

SCHEME 3.59 Synthesis of imidazo[1,2-

a

]pyridines through copper-catalyzed cyclization/oxidation process [65].

SCHEME 3.60 Generation of nitrogen-containing heterocycles through a 4-component coupling reaction [66].

SCHEME 3.61 Generation of indolylacetamides in an open vessel [67].

SCHEME 3.62 Preparation of amides from anilines and aldehydes [68].

SCHEME 3.63 Ruthenium-catalyzed synthesis of functionalized indoles [69].

SCHEME 3.64 Rhodium-catalyzed preparation of polyheteroaromatic compounds [70].

SCHEME 3.65 Palladium-catalyzed synthesis of indolines [71].

SCHEME 3.66 Metal-free synthesis of quinoxaline

N

-oxides [72].

SCHEME 3.67 Preparation of triazine oxides from propargylic oximes [73].

SCHEME 3.68 Dihydropyridazinone synthesis using a multicomponent reaction [74].

SCHEME 3.69 Synthesis of linked indoles [74].

SCHEME 3.70 Palladium-catalyzed synthesis of polycyclic indolines [75].

SCHEME 3.71 Synthesis of functionalized phosphonylpyrazoles through 1,3-dipolar cycloaddition reactions [76].

SCHEME 3.72 Synthesis of

N

-aryl phosphoramidates through the phosphoramidation of C‒H bonds [77].

SCHEME 3.73 Synthesis of functionalized pyrroles through an oxidative cyclization process [78].

SCHEME 3.74 Synthesis of functionalized pyrroles through titanium-mediated reactions [79].

SCHEME 3.75 Copper-catalyzed C‒H amidation of 2-phenylpyridine [80].

SCHEME 3.76 Synthesis of

O

-methyl hydroxamates from benzoic acid derivatives [81].

SCHEME 3.77 Conversion of poorly nucleophilic amines into amides under continuous flow conditions [82].

SCHEME 3.78 Synthesis of isoquinolones through rhodium-catalyzed annulation [81].

SCHEME 3.79 Metal-free annulation reactions between

O

-methyl hydroxamates and internal alkynes [83].

SCHEME 3.80 Rhodium-catalyzed hydration of nitriles [84].

SCHEME 3.81 Synthesis of tertiary amides through annulation [85].

SCHEME 3.82 Synthesis of functionalized indoles through a multicomponent reaction [86].

SCHEME 3.83 Synthesis of furoquinoxalines through a three-component coupling [87].

SCHEME 3.84 Synthesis of

N

-heterocyclic carbenes through a three-component coupling reaction [88].

SCHEME 3.85 Preparation of N-arylated phthalimides through carbonylation [89].

SCHEME 3.86 Preparation of isoquinolone using vinyl acetate as an acetylene equivalent [90].

SCHEME 3.87 Synthesis of indazole derivatives using copper catalysts [45].

SCHEME 3.88 Gold-catalyzed synthesis of indoles from ynamides [91].

SCHEME 3.89 Preparation of (

Z

)-3-methyleneisoindolin-1-ones [92].

SCHEME 3.90 Gold-catalyzed synthesis of imidazopyrimidines from ynamides [93].

SCHEME 3.91 Annulation of internal alkynes with naphthylcarbamates [94].

SCHEME 3.92 Copper-catalyzed synthesis of 3-aminopyrazoles from aryl hydrazides [95].

SCHEME 3.93 Copper-catalyzed synthesis of 4-iminopyrimines from

N

-phenylbenzimidamides [95].

SCHEME 3.94 Coupling primary amides with aryl halides using palladium catalysts [96].

SCHEME 3.95 One-pot synthesis of functionalized indoles [97].

SCHEME 3.96 Synthesis of pyrroles from benzonitriles [98].

SCHEME 3.97 Synthesis of 1,4-diaryl-1

H

-imidazoles from isocyanides [99].

SCHEME 3.98 Preparation of polysubstituted phenanthridines [100].

SCHEME 3.99 Regioselective synthesis of 2-nitroimidazopyridines [101].

SCHEME 3.100 Synthesis of 1,4-disubstituted pyrazoles [102].

SCHEME 3.101 Copper-catalyzed N-arylation of 1

H

-pyrazolo[3,4-

b

]pyridin-3-amine [103].

SCHEME 3.102 Synthesis of functionalized phenanthridines from 2-isocyanobiaryls [104].

SCHEME 3.103 Preparation of

N

-pyrrolylbenzimidazol-2-ones [105].

SCHEME 3.104 Synthesis of isoquinolones using visible light catalysis [106].

SCHEME 3.105 Preparation of polycyclic indoles through a two-step one-pot reaction [107].

SCHEME 3.106 Copper-catalyzed synthesis of heteroatom-rich pyrrolones [108].

SCHEME 3.107 Synthesis of linked triazoles [112].

SCHEME 3.108 Synthesis of triazoles under solvent-free conditions in air [113].

SCHEME 3.109 Synthesis of triazoles from methyl cinnamate under copper-free conditions [114].

SCHEME 3.110 Metal-free synthesis of a triazole in DMSO [116].

SCHEME 3.111 Metal-free synthesis of triazoles using the morpholinium/TsOH/BHT system [117].

SCHEME 3.112 Preparation of nitroarenes through nitration of arylboronic acids [118].

SCHEME 3.113 Copper-catalyzed synthesis of

N

-aryl sulfoximines [119].

SCHEME 3.114 Preparation of enamines through palladium-catalyzed cross-coupling [120].

SCHEME 3.115 Copper-catalyzed synthesis of enamides from primary amides [121].

SCHEME 3.116 Copper-catalyzed synthesis of enamides using a rubidium carbonate as the base [122].

SCHEME 3.117 Preparation of enamides using copper salts and DMEDA [123].

SCHEME 3.118 Coupling of a vinylboronic acid with benzimidazole [125].

SCHEME 3.119 N-vinylation of pyrimidines through copper-catalyzed cross-coupling [51].

SCHEME 3.120 Synthesis of vinyl nitrones using alkenylboronic acids [126].

SCHEME 3.121 Using alkenyltrifluoroborate salts in N-vinylation reactions [127].

SCHEME 3.122 Synthesis of enamides through vinyl transfer reactions [130].

SCHEME 3.123 Rhodium-catalyzed Markovnikov addition of aniline to phenylacetylene [135].

SCHEME 3.124 Gold-catalyzed Markovnikov hydroamination [136].

SCHEME 3.125 Ruthenium-catalyzed anti-Markovnikov hydroamination [137].

SCHEME 3.126 Nickel-catalyzed hydroamination of activated internal alkynes [138].

SCHEME 3.127 Rhodium-catalyzed anti-Markovnikov hydroamination of bulky anilines [139].

SCHEME 3.128 Z-selective anti-Markovnikov hydroamination using ruthenium catalysts [140].

SCHEME 3.129

E

-selective anti-Markovnikov hydroamination using ruthenium catalysts [140].

SCHEME 3.130 Gold-catalyzed synthesis of

Z

-enamides from propargyl aldehydes [141].

SCHEME 3.131 Acid-catalyzed enamide isomerization [141].

SCHEME 3.132 Base-assisted anti-Markovnikov hydroamination of phenylacetylene [142].

SCHEME 3.133 Synthesis of enamines with retention of an aryl bromide [143].

SCHEME 3.134 Preparation of

N

-tosyl-1,3-dien-2-yl amines from allenols [144].

SCHEME 3.135 Triphenylphosphine-catalyzed annulation reactions [145].

SCHEME 3.136 Palladium-catalyzed intramolecular hydroamination [146].

SCHEME 3.137 Rhodium-catalyzed preparation of

N

-heterocycles from benzamides [147].

SCHEME 3.138 Palladium-catalyzed preparation of amino-

N

-vinylindoles [148].

SCHEME 3.139 Preparation of tetrahydropyridines from dihydropyrans and anilines [149].

SCHEME 3.140 Synthesis of polycyclic systems from dihydropyrans [149].

SCHEME 3.141 Rhodium-catalyzed synthesis of azomethine ylides and their use in multicomponent reactions [150].

SCHEME 3.142 Preparation of pyrazolines through copper-catalyzed cycloaddition reactions [151].

SCHEME 3.143 Nitration of a vinylboronic acid using bismuth nitrate [118].

SCHEME 3.144 BuLi-promoted synthesis of ynamides [159].

SCHEME 3.145 Synthesis of ynamides from phenyl(trimethylsilylethynyl)iodonium triflate [162].

SCHEME 3.146 Metal-free synthesis of ynamides [163].

SCHEME 3.147 Synthesis of ynamides from

gem

-dibromoalkenes [164].

SCHEME 3.148 Copper-promoted coupling of terminal alkynes with secondary amides [165].

SCHEME 3.149 Copper-catalyzed synthesis of ynamides from haloalkynes [166].

SCHEME 3.150 Synthesis of a macrocyclic ynamide [169].

SCHEME 3.151 Copper-catalyzed synthesis of ynindoles [176].

Chapter 04

FIGURE 4.1 Common approaches to the synthesis of organophosphines.

SCHEME 4.1 Preparation of

t

Bu

2

PCl through treatment of PCl

3

with a Grignard reagent [4].

SCHEME 4.2 Modification of the Grignard approach for the preparation of alkylphosphines [7].

SCHEME 4.3 Preparation of a bulky alkylphosphine using a Grignard approach [10].

SCHEME 4.4 Synthesis of alkylphosphines using a potassium phosphide [16].

SCHEME 4.5 Synthesis of borane-protected bisphosphine [21].

SCHEME 4.6 Ruthenium-catalyzed synthesis of P-chiral phosphines [23].

SCHEME 4.7 Ruthenium-catalyzed synthesis of bisphosphines [23].

SCHEME 4.8 Synthesis of alkylphosphines from secondary phosphine oxides [24].

SCHEME 4.9 Synthesis of an alkylphosphine from a benzyl alcohol [25].

SCHEME 4.10 Palladium-catalyzed asymmetric synthesis of C-chiral monodentate phosphines [26].

SCHEME 4.11 Platinum-catalyzed phosphorus–carbon bond-forming reactions [28].

SCHEME 4.12 Alkoxide-mediated addition of secondary phosphine oxides to alkenes [55].

SCHEME 4.13 Synthesis of bisphosphines bearing electron-withdrawing groups [16].

SCHEME 4.14 Addition of secondary phosphines to styrene derivatives [56].

SCHEME 4.15 Hydrophosphination of an air-stable primary phosphine [57].

SCHEME 4.16 Synthesis of bisphosphines through a double hydrophosphination process [58].

SCHEME 4.17 Metal-free addition of silylphosphines to vinyl pyridines [59].

SCHEME 4.18 TBAF-promoted addition of silylphosphines to a tetrasubstituted alkene [59].

SCHEME 4.19 Rhodium-catalyzed addition of silylphosphines to alkenes [61].

SCHEME 4.20 Calcium-catalyzed synthesis of alkylphosphines [62].

SCHEME 4.21 Barium-promoted addition of secondary phosphines to styrene [63].

SCHEME 4.22 Copper-catalyzed synthesis of alkylphosphine oxides in water [65].

SCHEME 4.23 Iron-catalyzed addition of diphenylphosphine to alkenes [66].

SCHEME 4.24 Enantioselective addition of secondary phosphines to alkenes [64].

SCHEME 4.25 Palladium-catalyzed dual addition of secondary phosphines [75].

SCHEME 4.26 Nickel-catalyzed asymmetric synthesis of alkylphosphines through hydrophosphinylation [76, 77].

SCHEME 4.27 Use of a P-stereogenic PCP pincer ligand in asymmetric hydrophosphination reactions [20].

SCHEME 4.28 Uncatalyzed addition of secondary phosphine oxides to styrene derivatives [78].

SCHEME 4.29 Hydrophosphination with Markovnikov and anti-Markovnikov selectivity [80].

SCHEME 4.30 Addition of secondary phosphines to imines [81].

SCHEME 4.31 Addition of phosphines to alkynes followed by trapping with an aldehyde to generate zwitterionic phosphonium enolates [83].

SCHEME 4.32 Photochemical addition of phosphonium salts to alkenes [84].

SCHEME 4.33 Addition of secondary phosphine oxides to alkenes under photochemical conditions [85].

SCHEME 4.34 Addition of phosphinyl radicals to vinyl ethers [86].

SCHEME 4.35 Tin-free addition of phosphinyl radicals to vinyl ethers [86].

SCHEME 4.36 Addition of secondary phosphine oxides to an allylic alcohol using visible light catalysis [87].

SCHEME 4.37 Benzoic acid promoted synthesis of α-aminophosphine oxides [88].

SCHEME 4.38 Synthesis of heterocycles bearing phosphine oxide pendant groups [89].

SCHEME 4.39 Synthesis of α-aminophosphine oxides [90].

SCHEME 4.40 Decarboxylative approach to the synthesis of α-aminophosphine oxides [91].

SCHEME 4.41 Synthesis of imidoylphosphine oxides [92].

SCHEME 4.42 Addition of secondary phosphines to imines using a magnesium catalyst [93].

SCHEME 4.43 Addition of diphenylphosphine oxide to isocyanides [94].

SCHEME 4.44 Synthesis of functionalized alkylphosphine oxides [95].

SCHEME 4.45 Use of a CO

2

-trapped carbene as a precatalyst for the addition of secondary phosphine oxides to activated alkenes [96].

SCHEME 4.46 Tandem CP bond-forming/olefination reactions [98].

SCHEME 4.47 Preparation of a functionalized ribose through Arbuzov chemistry [99].

SCHEME 4.48 Synthesis of allylphosphonates using Arbuzov chemistry [100].

SCHEME 4.49 Synthesis of Ethephon through phosphorus-carbon(sp

3

) bond formation/hydrolysis [101].

SCHEME 4.50 Functionalization of sugars through Arbuzov chemistry [102].

SCHEME 4.51 Lewis acid-assisted synthesis of benzylphosphonates [104].

SCHEME 4.52 Lewis acid-assisted synthesis of allylphosphonates [104].

SCHEME 4.53 Lewis acid-assisted conversion of alkyl halides into alkylphosphonates [105].

SCHEME 4.54 Lewis acid conversion of alcohols into alkylphosphonates [105].

SCHEME 4.55 Synthesis of alkylphosphonates through base-assisted Michaelis–Becker reactions [106].

SCHEME 4.56 Michaelis–Becker synthesis of functionalized purines [107].

SCHEME 4.57 Cesium carbonate-promoted Michaelis–Becker reactions [108].

SCHEME 4.58 Potassium carbonate-promoted Michaelis–Becker reactions [108].

SCHEME 4.59 Using NaHMDS as the base in the synthesis of propargylphosphonates [110].

SCHEME 4.60 Using KHMDS in the synthesis of benzylphosphonates [111].

SCHEME 4.61 Preparation of nucleoside-derived alkylphosphonates [112].

SCHEME 4.62 Palladium-catalyzed synthesis of nucleoside-derived benzylphosphonates [113, 114].

SCHEME 4.63 Conversion of

N

-tosylhydrazones into alkylphosphonates [95].

SCHEME 4.64 Potassium carbonate-promoted

phospha

-Michael reactions [117].

SCHEME 4.65 Tetramethylguanidine-promoted

phospha

-Michael reactions [118].

SCHEME 4.66 DBU-promoted

phospha

-Michael reactions [119].

SCHEME 4.67 Sodium hydride-promoted

phospha

-Michael reactions [120, 121].

SCHEME 4.68 LDA-promoted

phospha

-Michael reactions [121].

SCHEME 4.69 Calcium oxide-promoted

phospha

-Michael reactions [122].

SCHEME 4.70 Selective addition of secondary phosphites to alkenes in the presence of carbonyl groups [123].

SCHEME 4.71

Phospha

-Michael additions with retention of chirality [124].

SCHEME 4.72

Phospha

-Michael additions using carbene catalysts [96].

SCHEME 4.73 Synthesis of alkylphosphonates from aldehyde-containing alkenes [125–127].

SCHEME 4.74 Radical addition of diethylphosphite to enopyranoses [128].

SCHEME 4.75 Manganese acetate-promoted addition of phosphites to alkenes [129].

SCHEME 4.76 Synthesis of nitrogen heterocycles with tethered phosphonate groups [89].

SCHEME 4.77 Nickel-catalyzed hydrophosphinylation [130].

SCHEME 4.78 Nickel-catalyzed preparation of phosphorus-containing heterocycles [130].

SCHEME 4.79 Radical phosphonofluorination of alkenes [131].

SCHEME 4.80 Rhodium-catalyzed addition of phosphites to unactivated alkenes [132].

SCHEME 4.81 Asymmetric addition of phosphites to norbornene [133].

SCHEME 4.82 Hydrophosphonylation of unfunctionalized cyclopropenes [134].

SCHEME 4.83 Hydrophosphonylation of amide-functionalized cyclopropenes [134].

SCHEME 4.84 Radical addition to unactivated alkenes [124].

SCHEME 4.85 Diastereoselective synthesis of α-aminophosphonates [158].

SCHEME 4.86 Synthesis of β-phthalimide-α-hydroxyphosphonates [159].

SCHEME 4.87 Uncatalyzed addition of secondary phosphites to imines [160].

SCHEME 4.88 Use of an iron-based heterogeneous catalyst for the formation of α-aminophosphonates [161].

SCHEME 4.89 Conversion of chlorophosphites into α-aminophosphonates [162].

SCHEME 4.90 Acid-catalyzed ultrasound-promoted synthesis of α-aminophosphonates [163].

SCHEME 4.91 Ultrasound-assisted uncatalyzed synthesis of α-aminophosphonates [164].

SCHEME 4.92 Preparation of α-aminophosphonates through reductive phosphonylation [90].

SCHEME 4.93 Synthesis of α-aminophosphonates in water [165].

SCHEME 4.94 Synthesis of α-aminophosphonates through CH activation [166].

SCHEME 4.95 Copper-catalyzed synthesis of α-aminophosphonates [91].

SCHEME 4.96 Benzoic acid-catalyzed synthesis of α-aminophosphonates [88].

SCHEME 4.97 Synthesis of α-aminophosphonates using supported tantalum salts [156].

SCHEME 4.98 Preparation of α-aminophosphonates using Yb(OTf)

3

[168].

SCHEME 4.99 Samarium iodide-catalyzed synthesis of α-aminophosphonates [169].

SCHEME 4.100 Scandium triflate-catalyzed synthesis of α-aminophosphonates [170].

SCHEME 4.101 Preparation of α-aminophosphonate using (bromodimethyl)sulfonium bromide as the catalyst [171].

SCHEME 4.102 InCl

3

-catalyzed conversion of aldehydes into α-aminophosphonates [172].

SCHEME 4.103 Conversion of ketones into α-aminophosphonates using InCl

3

as the catalyst [172].

SCHEME 4.104 Synthesis of α-aminophosphonates from sulfones [173].

SCHEME 4.105 Synthesis of α-aminophosphonates using elemental indium as the catalyst precursor [174].

SCHEME 4.106 Sulfuric acid-promoted synthesis of α-aminophosphonates [175].

SCHEME 4.107 Synthesis of α-aminophosphonates through photoredox process [178].

SCHEME 4.108 Preparation of alkylphosphonates promoted by visible light [179].

SCHEME 4.109 A dehydrogenative coupling approach to the synthesis of α-aminophosphonates [180].

SCHEME 4.110 CH phosphorylation of dimethyl anilines [182].

SCHEME 4.111 PEG-promoted synthesis of α-aminophosphonates [183].

SCHEME 4.112 Decarboxylative approach to the synthesis of α-aminophosphonates [184].

SCHEME 4.113 Asymmetric synthesis of α-aminophosphonates [185].

SCHEME 4.114 Phosphoric acid-catalyzed asymmetric synthesis of α-aminophosphonates [186].

SCHEME 4.115 Organocatalyzed asymmetric addition of phosphites to imines [187].

SCHEME 4.116 Preparation of chiral α-aminophosphonates containing a quaternary stereocenter adjacent to the phosphonate [194].

SCHEME 4.117 Organocatalyzed approach to the synthesis of chiral α-aminophosphonates bearing a quaternary stereocenter [195].

SCHEME 4.118 Organocatalyzed enantioselective synthesis of α-aminophosphonates [196].

SCHEME 4.119 Asymmetric addition of a lithium phosphonate to ketosulfinimines [197].

SCHEME 4.120 Copper-catalyzed enantioselective addition of phosphites to ketimines [198].

SCHEME 4.121 Enantioselective addition of phosphites to aldimines catalyzed by aluminum salen complex [201].

SCHEME 4.122 Asymmetric addition of phosphites to imines using a multimetallic catalyst along with (

R

)-BINOL [202].

SCHEME 4.123 Asymmetric addition of phosphites to cyclic aldimines catalyzed by an ytterbium/potassium complex along with (R)-BINOL [203].

SCHEME 4.124 Asymmetric synthesis of α-aminophosphonates at low catalyst loadings [205].

SCHEME 4.125 Asymmetric synthesis of α-aminophosphonates using scandium triflate along with a chiral supporting ligand [206].

SCHEME 4.126 Synthesis of β-aminophosphonates through an Arbuzov process [207, 208].

SCHEME 4.127 Preparation of β-aminophosphonates using an acyclic amide protecting group [209].

SCHEME 4.128 Asymmetric synthesis of β-aminophosphonates through the ring opening of aziridines [210].

SCHEME 4.129 Organocatalytic approach to the synthesis of alkylphosphonates with multiple chiral centers [211].

SCHEME 4.130 Barium hydroxide-promoted addition of phosphites to aldehydes [224].

SCHEME 4.131 Microwave-assisted synthesis of α-hydroxyphosphine oxides [226].

SCHEME 4.132 Synthesis of phosphorylated nucleosides [227].

SCHEME 4.133 Synthesis of α-hydroxyphosphonates through Pudovick-type chemistry [228].

SCHEME 4.134 Solvent-free synthesis of α-hydroxyphosphonates [229].

SCHEME 4.135 Calcium-catalyzed synthesis of α-hydroxyphosphonates from aldehydes [230].

SCHEME 4.136 Calcium-catalyzed synthesis of α-hydroxyphosphonates from ketones [230].

SCHEME 4.137 Calcium oxide-promoted synthesis of α-hydroxyphosphonates [122].

SCHEME 4.138 Preparation of α-hydroxyphosphonates using a lanthanum-based catalyst [231].

SCHEME 4.139 Synthesis of α-hydroxyphosphonates from aldehydes using sodium-modified fluorapatite [232].

SCHEME 4.140 Synthesis of α-hydroxyphosphonates from ketones using sodium-modified fluorapatite [232].

SCHEME 4.141 Microwave-assisted synthesis of α-hydroxyphosphonates [226].

SCHEME 4.142 Ultrasound-promoted synthesis of α-hydroxyphosphonates [163].

SCHEME 4.143 Preparation of α-hydroxyphosphonates using ultrasound and potassium dihydrogenphosphate [233].

SCHEME 4.144 Synthesis of α-hydroxyphosphonates in water [183].

SCHEME 4.145 Asymmetric synthesis of α-hydroxyphosphonates using an aluminum-based catalyst [235].

SCHEME 4.146 Asymmetric synthesis of α-hydroxyphosphonates from aliphatic aldehydes using an aluminum-based catalyst [237].

SCHEME 4.147 Asymmetric synthesis of α-hydroxyphosphonates from benzaldehydes using an aluminum-based catalyst [237].

SCHEME 4.148 Enantioselective synthesis of α-hydroxyphosphonates bearing a trifluoromethyl group [238].

SCHEME 4.149 Asymmetric synthesis of hydroxyphosphonates using P(OMnt)

3

[212].

SCHEME 4.150 A multicomponent approach to the asymmetric synthesis of α-hydroxyl phosphonates [239].

SCHEME 4.151 Asymmetric synthesis of α-hydroxyphosphonates using a samarium-based catalyst [240].

SCHEME 4.152 Preparation of resolved α-hydroxyphosphonates using an iron-based catalyst [241].

SCHEME 4.153 Asymmetric addition of phosphites to aldehydes catalyzed by an ytterbium-based catalyst [205].

SCHEME 4.154 Enantioselective synthesis of α-hydroxyphosphonates [201, 242].

SCHEME 4.155 Enantioselective synthesis of α-hydroxyphosphonates from aldehydes using triaminoiminophosphorane-based catalysts [245].

SCHEME 4.156 Enantioselective synthesis of α-hydroxyphosphonates from ynones [246].

SCHEME 4.157 Iron-catalyzed synthesis of β-hydroxyphosphonates from alkenes [247].

SCHEME 4.158 Organocatalytic additions of diarylphosphites to α-keto esters [248].

SCHEME 4.159 Conversion of α-hydroxyphosphonates into alkyl bromides [249].

SCHEME 4.160 Conversion of α-hydroxyphosphonates into alkyl azides [249].

SCHEME 4.161 Microwave-assisted synthesis of bisphosphonic acid [250].

SCHEME 4.162 Chemoselective synthesis of bisphosphonates from acyl chlorides [251].

SCHEME 4.163 Synthesis of a tagged bisphosphonic acid derivative [252].

SCHEME 4.164 Synthesis of bisphosphonic acids from an acyl chloride [253].

SCHEME 4.165 Synthesis of bisphosphonic acids from carboxylic acids [254].

SCHEME 4.166 Preparation of a bile salt-functionalized bisphosphonic acid [255].

SCHEME 4.167 Preparation of an amine-linked bisphosphonate species [256].

SCHEME 4.168 Preparation of bisphosphonates from aniline precursors [257].

SCHEME 4.169 Preparation of bisphosphonates from dichloromethane [258].

SCHEME 4.170 Synthesis of a mixed bisphosphorus species [259].

SCHEME 4.171 Conversion of a bisphosphonate into a trisphosphonate [260].

SCHEME 4.172 Preparation of the phosphorus-containing heterocycle [261].

SCHEME 4.173 Synthesis of a triarylphosphine using a Grignard approach [263].

SCHEME 4.174 Enabling the use of electrophile-containing aryl halides in the synthesis of triarylphosphines [6].

SCHEME 4.175 Phosphination of a brominated metallocene [271].

SCHEME 4.176 Fluoride-mediated synthesis of arylphosphines from aryl fluorides [280].

SCHEME 4.177 Palladium-catalyzed synthesis of arylphosphines [281].

SCHEME 4.178 Effect of solvent on the stereochemical outcome of the phosphination reaction [286].

SCHEME 4.179 Palladium-catalyzed cross-coupling of aryl chlorides with secondary phosphines [288].

SCHEME 4.180 Microwave-assisted palladium-catalyzed synthesis of an az α-BINAP derivative [291].

SCHEME 4.181 Microwave-assisted phosphination of a ruthenocene derivative [271].

SCHEME 4.182 Using arenediazonium salts as substrates for the palladium-catalyzed synthesis of arylphosphines [292].

SCHEME 4.183 Preparation of the 2,2-bis(diphenylphosphino)biphenyls through cross-coupling [293].

SCHEME 4.184 Phosphination of deoxyuridine using a cross-coupling approach [294].

SCHEME 4.185 Palladium-catalyzed phosphination of arylnonaflates [295].

SCHEME 4.186 Aryl–aryl exchange between palladium and phosphorus [309].

SCHEME 4.187 Synthesis of arylphosphines using PPh

3

as the phosphinating agent [310, 311].

SCHEME 4.188 Synthesis of phospholes through an aryl–aryl exchange reaction [316].

SCHEME 4.189 Synthesis of phosphacycles through a palladium-mediated exchange reaction [317].

SCHEME 4.190 Copper-catalyzed synthesis of arylphosphines using a CuI/dmed catalyst system [318].

SCHEME 4.191 Copper-catalyzed synthesis of arylphosphines using reduction as the first step [24].

SCHEME 4.192 Synthesis of a borane-protected 1-phenyl-2-oxa-1-phosphindane [330].

SCHEME 4.193 P-arylation of arynes [332].

SCHEME 4.194 Synthesis of crowded phosphine oxides [333].

SCHEME 4.195 Reactivity of dimesitylphosphine oxide with diaryliodonium reagents [333].

SCHEME 4.196 Palladium-catalyzed coupling of arenediazonium salts with secondary phosphine oxides [292].

SCHEME 4.197 Nickel-catalyzed conversion of a phenol into a phosphine oxide using PyBroP as a promoter [334].

SCHEME 4.198 Microwave-assisted palladium-catalyzed coupling of secondary phosphine oxides with aryl triflates [335].

SCHEME 4.199 Nickel-catalyzed coupling of aryl bromides and chlorides with secondary phosphine oxides [336].

SCHEME 4.200 Synthesis of phosphine oxides through cross-coupling using (DME)NiCl

2

as the catalyst [337].

SCHEME 4.201 Synthesis of phosphine oxides through cross-coupling using (Ph

3

P)NiCl

2

as the catalyst [337].

SCHEME 4.202 Preparation of phosphine oxides in water using nickel catalysts [338].

SCHEME 4.203 Palladium-catalyzed synthesis of arylphosphine oxides in water [339].

SCHEME 4.204 Using palladacycles to promote the cross-coupling reaction in water [340].

SCHEME 4.205 Nickel-catalyzed synthesis of arylphosphine oxides from aryl mesylates [341].

SCHEME 4.206 Palladium-catalyzed synthesis of arylphosphine oxides through CH activation [342].

SCHEME 4.207 Palladium-catalyzed coupling of secondary phosphine oxides with iodinated heterocycles [345].

SCHEME 4.208 Nickel-catalyzed cross-coupling of arylboronic acids with secondary phosphine oxides [346].

SCHEME 4.209 Selective synthesis of unsymmetrical phosphine sulfides [347].

SCHEME 4.210 Synthesis of an arylphosphonate using an ortho-metallation approach [351].

SCHEME 4.211 Synthesis of arylphosphinates through the addition of diethylphenylphosphite to arynes [332].

SCHEME 4.212 Synthesis of arylphosphonates through the addition of phosphites to arynes [332].

SCHEME 4.213 Metal-free microwave-assisted synthesis of arylphosphonates [352].

SCHEME 4.214 Metal-free phosphorylation of purines [353].

SCHEME 4.215 Chemoselective phosphorylation of mixed halide species [354].

SCHEME 4.216 Metal-free synthesis of pyridylphosphonates [355].

SCHEME 4.217 Preparation of pyridylphosphonates using pyridinium salts [357].

SCHEME 4.218 Nickel-catalyzed synthesis of arylphosphonates from trialkylphosphites [365].

SCHEME 4.219 Nickel bromide-catalyzed synthesis of arylphosphonates [366].

SCHEME 4.220 Nickel chloride-promoted synthesis of arylphosphonates using KBr as an additive [367].

SCHEME 4.221 Classic Hirao coupling [368, 369].

SCHEME 4.222 Palladium-catalyzed synthesis of arylphosphonates using potassium acetate as an additive [377].

SCHEME 4.223 Synthesis of arylphosphonates from aryl chlorides using DMF as the solvent [379].

SCHEME 4.224 Palladium-catalyzed cross-coupling of aryl chlorides with hydrogen phosphinate esters [380].

SCHEME 4.225 Synthesis of arylphosphonates in an organic solvent using a palladacycle-based catalyst [109].

SCHEME 4.226 Synthesis of arylphosphonates in water using a palladacycle-based catalyst [340].

SCHEME 4.227 Microwave-assisted palladium-catalyzed synthesis of arylphosphonates [381].

SCHEME 4.228 Preparation of a nucleoside-derived arylphosphonate [381].

SCHEME 4.229 Synthesis of crowded arylphosphonates [387].

SCHEME 4.230 Synthesis of multiple aryl groups through sequential functionalizations [387].

SCHEME 4.231 Synthesis of arylphosphonates at low temperatures [388].

SCHEME 4.232 Low-temperature coupling of aryl halides with secondary phosphites [389].

SCHEME 4.233 Synthesis of arylphosphonates from aryl imidazolylsulfonates [390].

SCHEME 4.234 Palladium-catalyzed coupling of arylboronic acids with secondary phosphites [391].

SCHEME 4.235 Palladium-catalyzed synthesis of arylphosphonates from aryl triflates [392].

SCHEME 4.236 Microwave-assisted synthesis of a progesterone-derived arylphosphonate [335].

SCHEME 4.237 Palladium-catalyzed synthesis of arylphosphonates in ethanol [393].

SCHEME 4.238 Conversion of arenediazonium salts into arylphosphonates [292].

SCHEME 4.239 One-pot conversion of anilines into arylphosphonates through the formation of arenediazonium salts [292].

SCHEME 4.240 Palladium-catalyzed synthesis of phosphonylated heterocycles [345].

SCHEME 4.241 Copper-catalyzed synthesis of arylphosphonates [318].

SCHEME 4.242 Using iodonium salts in the copper-catalyzed synthesis of arylphosphonates [333].

SCHEME 4.243 Nickel-catalyzed coupling of secondary phosphites with aryl halides [336].

SCHEME 4.244 Synthesis of arylphosphonates through nickel-catalyzed cross-coupling [341].

SCHEME 4.245 Nickel-catalyzed synthesis of arylphosphonates from phenols [334].

SCHEME 4.246 CH phosphorylation of mesitylene [401].

SCHEME 4.247 Manganese(III) acetate-promoted phosphonation of heteroarenes [403].

SCHEME 4.248 Regioselective formation of arylphosphonates [404].

SCHEME 4.249 Synthesis of arylphosphonates in air [404].

SCHEME 4.250 Preparation of pyrimidylphosphonates [405].

SCHEME 4.251 Synthesis of arylphosphonates from heteroarenes [406].

SCHEME 4.252 Synthesis of pyridylphosphonates from heteroarenes [406].

SCHEME 4.253 Synthesis of arylphosphonates through CH phosphonylation [407].

SCHEME 4.254 Selective phosphonylation of unfunctionalized indoles [408].

SCHEME 4.255 Pyridylphosphonate synthesis through palladium-catalyzed CH activation [342].

SCHEME 4.256 Heteroarylphosphonate synthesis through palladium-catalyzed CH activation [409].

SCHEME 4.257 Synthesis of arylphosphonates through CH activation [410].

SCHEME 4.258 Copper-catalyzed synthesis of arylphosphonates using arylboronic acids in air [411].

SCHEME 4.259 Nickel-catalyzed coupling of arylboronic acids with secondary phosphites in air [346].

SCHEME 4.260 Synthesis of a chiral phosphine [412].

SCHEME 4.261 Synthesis of a fluorinated trivinylphosphine [427].

SCHEME 4.262 Synthesis of vinylphosphines using protected chlorophosphines [8].

SCHEME 4.263 Synthesis of divinyl phenylphosphine [428].

SCHEME 4.264 Synthesis of vinylphosphines using an α-substituted vinyl Grignard reagent [262].

SCHEME 4.265 Synthesis of a crowded vinylchlorophosphine using a Grignard approach [430].

SCHEME 4.266 Synthesis of a crowded vinylphosphine [429].

SCHEME 4.267 Synthesis of a crowded secondary phosphine [432].

SCHEME 4.268 Synthesis of a fluorinated vinylphosphine [433].

SCHEME 4.269 Modification of the reactivity of vinyl Grignard reagents through the formation of organocopper species [8].

SCHEME 4.270 Synthesis of vinylphosphines using lithium phosphides [434].

SCHEME 4.271 Metal-free synthesis of vinylphosphines [7].

SCHEME 4.272 Synthesis of vinylphosphines and subsequent reaction with methyl iodide [436].

SCHEME 4.273 Synthesis of allylphosphines and subsequent reaction with sulfur [436].

SCHEME 4.274 Synthesis of vinylphosphines through palladium-catalyzed cross-coupling chemistry [437].

SCHEME 4.275 Synthesis of vinylphosphines through cross-coupling [7].

SCHEME 4.276 Palladium-catalyzed synthesis of protected vinylphosphines from vinyl triflates [295].

SCHEME 4.277 Use of vinyl triflates as substrates in the palladium-catalyzed synthesis of vinylphosphines [439, 440].

SCHEME 4.278 Using vinyl triflates and related compounds in the palladium-catalyzed synthesis of vinylphosphines [441, 442].

SCHEME 4.279 Synthesis of functionalized vinylphosphine oxides through cross-coupling [443].

SCHEME 4.280 Synthesis of a chiral phosphine from a vinylphosphine oxide [444].

SCHEME 4.281 Synthesis of protected vinylphosphines from enol phosphates [447].

SCHEME 4.282 Synthesis of vinylphosphines through nickel-catalyzed cross-coupling [448].

SCHEME 4.283 Synthesis of vinylphosphines through copper-catalyzed cross-coupling [318].

SCHEME 4.284 Synthesis of vinylphosphines using a nickel/zinc catalyst system [329].

SCHEME 4.285 Synthesis of vinylphosphines through a base-assisted addition reaction [449].

SCHEME 4.286 Addition of sodium phosphide to an alkyne [73].

SCHEME 4.287 Addition of a protected secondary phosphine to an alkyne [450].

SCHEME 4.288 Base-catalyzed addition of a primary phosphine to an activated alkyne [451].

SCHEME 4.289 Addition of secondary phosphines to internal alkynes [453, 454].

SCHEME 4.290 Addition of protected secondary phosphines to internal alkynes [455, 456].

SCHEME 4.291 Addition of protected secondary phosphines to propargyl alcohols [455, 456].

SCHEME 4.292 Radical addition of secondary phosphines to alkynes [458].

SCHEME 4.293 Addition of tetraorganodiphosphines to alkynes [459].

SCHEME 4.294 Silver-promoted annulation reaction between secondary phosphine oxides and internal alkynes [460].

SCHEME 4.295 Base-catalyzed intramolecular hydrophosphinylation [461].

SCHEME 4.296 Conversion of 1,1-dibromoalkenes into vinylphosphine oxides [462].

SCHEME 4.297 Synthesis of bisvinylphosphines through addition reactions [463].

SCHEME 4.298 Using trispyridylphosphine in addition reactions with activated alkynes [465].

SCHEME 4.299 Synthesis of vinylphosphines using calcium catalysts [62].

SCHEME 4.300 Double addition of diphenylphosphine to conjugated diynes [466, 467].

SCHEME 4.301 Using calcium and ytterbium compounds as catalysts for hydrophosphination reactions [468].

SCHEME 4.302 Copper-catalyzed synthesis of vinylphosphines from secondary phosphines [469].

SCHEME 4.303 Selective addition of a secondary phosphine to diphenylacetylene [470].

SCHEME 4.304 Palladium-catalyzed addition of protected secondary phosphines to alkynes [450].

SCHEME 4.305 Synthesis of chiral-borane protected vinylphosphines [471].

SCHEME 4.306 Regio- and stereoselective synthesis of vinylphosphines [472].

SCHEME 4.307 Rhodium-catalyzed addition of silylphosphines to propargyl alcohols [61].

SCHEME 4.308 Synthesis of vinylphosphine oxides through a ruthenium-catalyzed process [473].

SCHEME 4.309 Palladium-catalyzed addition of tetraorganophosphines to terminal alkynes [474, 475].

SCHEME 4.310 Synthesis of 1,1-diphosphinoethenes [476].

SCHEME 4.311 Thiophosphination of a terminal alkyne [477].

SCHEME 4.312 Copper-promoted conversion of vinylzirconocenes into protected vinylphosphines [478].

SCHEME 4.313 Copper-promoted conversion of α-substituted vinyl zirconocenes into crowded vinylphosphines through the addition of Na

2

(dtc) [478].

SCHEME 4.314 Zirconocene-mediated synthesis of vinylphosphines [416].

SCHEME 4.315 Synthesis of a C

2

-symmetric bisphosphine [479].

SCHEME 4.316 Synthesis of acylphosphines [480].

SCHEME 4.317 Palladium-catalyzed double addition of triphenylphosphine to diynes [481].

SCHEME 4.318 Rhodium-catalyzed addition of triphenylphosphine to alkynes [481].

SCHEME 4.319 Synthesis of frustrated Lewis acid–base pairs [433].

SCHEME 4.320 Application of a bisphosphine oxide as an organocatalyst [479].

SCHEME 4.321 Copper oxide-catalyzed decarboxylative CP cross-coupling [482].

SCHEME 4.322 Copper chloride-catalyzed decarboxylative CP cross-coupling [483].

SCHEME 4.323 Synthesis of a highly functionalized vinylphosphinate [484].

SCHEME 4.324 Nickel-catalyzed addition of secondary phosphine oxides to propargyl alcohols leading to the formation of 1,3-butadienes [485].

SCHEME 4.325 Copper iodide-catalyzed addition of secondary phosphine oxides to internal and terminal alkynes [486].

SCHEME 4.326 Copper acetylacetonate-catalyzed addition of secondary phosphine oxides to propargyl alcohols and internal alkynes [487].

SCHEME 4.327 Rhodium-catalyzed addition of secondary phosphine oxides to terminal alkynes [488].

SCHEME 4.328 Rhodium-catalyzed addition of chiral secondary phosphine oxides to terminal alkynes [489].

SCHEME 4.329 Palladium-catalyzed addition of secondary phosphine oxides to terminal alkynes [490].

SCHEME 4.330 Phosphine-catalyzed addition of secondary phosphine oxides to activated alkynes [491].

SCHEME 4.331 Palladium-catalyzed addition of secondary phosphine oxides to isocyanides [94].

SCHEME 4.332 Synthesis of vinylphosphonates through palladium-catalyzed cross-coupling [493].

SCHEME 4.333 Synthesis of vinylphosphonates through copper iodide-catalyzed cross-coupling [318].

SCHEME 4.334 Copper-catalyzed coupling of secondary phosphites with vinyl bromides [497].

SCHEME 4.335 Copper-catalyzed coupling of secondary phosphites with iodonium salts [498].

SCHEME 4.336 Palladium-catalyzed vinylphosphonate-linked nucleosides [499].

SCHEME 4.337 Copper-catalyzed decarboxylative synthesis of vinylphosphonates and phosphinates [482].

SCHEME 4.338 Palladium-catalyzed coupling of secondary phosphites with boronic acids [391].

SCHEME 4.339 Palladium-catalyzed PH addition reactions [500].

SCHEME 4.340 Phosphine-catalyzed PH addition reactions [491].

SCHEME 4.341 Palladium-catalyzed PH addition reactions using a resolved phosphinate [501].

SCHEME 4.342 Copper-catalyzed PH addition reactions using phenylacetylene [487].

SCHEME 4.343 Palladium-catalyzed Markovnikov-selective PH addition reactions [502].

SCHEME 4.344 Synthesis of an acylphosphonate [503, 504].

SCHEME 4.345 Synthesis of 1-hydroxyiminophosphonates [505].

SCHEME 4.346 Nickel-catalyzed coupling of chlorophosphines with terminal alkynes [522].

SCHEME 4.347 Stepwise approach to the synthesis of a phosphinated propargyl alcohol [469].

SCHEME 4.348 Oxidative alkynylation with borane protection of the resulting alkynylphosphines [523].

SCHEME 4.349 Oxidative alkynylation of borane-phosphines using a functionalized organocopper reagent [523].

SCHEME 4.350 Copper-catalyzed coupling of protected secondary phosphines with terminal alkynes [524].

SCHEME 4.351 Copper-catalyzed synthesis of protected alkynylphosphines using a preformed copper catalyst [525].

SCHEME 4.352 Synthesis of an alkynylphosphine oxide followed by conversion into a triazole [526].

SCHEME 4.353 Synthesis and application of an alkynylphosphine oxide [537].

SCHEME 4.354 Synthesis of a crowded alkynylphosphine oxide [529].

SCHEME 4.355 Successful phosphinylation of a nitro-substituted arylalkyne [528].

SCHEME 4.356 Synthesis and application of an ethynylphosphine oxide [536].

SCHEME 4.357 Synthesis of alkynylphosphine oxides through a decarboxylative coupling reaction [482].

SCHEME 4.358 Synthesis of a CATPHOS-type ligand from an alkynylphosphine oxide [538].

SCHEME 4.359 Synthesis and application of an alkynylphosphine oxide as an organocatalyst [539].

SCHEME 4.360 Alkynylation of secondary phosphine oxides using iodonium species [541].

SCHEME 4.361 Synthesis of a crowded alkynylphosphonate [529].

SCHEME 4.362 Synthesis of a mifepristone-derived alkynylphosphonate [544].

SCHEME 4.363 Synthesis of alkynylphosphonates from 1,1-dibromoalkenes [545].

SCHEME 4.364 Copper-catalyzed oxidative coupling of terminal alkynes with secondary phosphites [517].

SCHEME 4.365 Synthesis of an alkynylphosphonate through an oxidative coupling reaction [550].

SCHEME 4.366 Decarboxylative synthesis of an alkynylphosphonate [551].

SCHEME 4.367 Transition metal-free synthesis of alkynylphosphonates in open vessels [541].

Chapter 05

SCHEME 5.1 Synthesis of alkyl aryl sulfides using Na

2

S

2

O

3

as a sulfurating agent [1].

SCHEME 5.2 Palladium-catalyzed hydrothiolation of vinyl ethers [2].

SCHEME 5.3 Trifluoromethylthiolation of alkylboronic acids [3].

SCHEME 5.4 Thia-Michael reaction in water [4].

SCHEME 5.5 Enantioselective thia-Michael reactions [6].

SCHEME 5.6 Enantioselective addition of thioacetic acid to activated alkenes [7].

SCHEME 5.7 Organocatalyzed asymmetric thia-Michael addition reactions [8].

SCHEME 5.8 Asymmetric sulfenylation of silyl enol ethers [9].

SCHEME 5.9 Iron-catalyzed thia-Michael additions [10].

SCHEME 5.10 Carbene-promoted thia-Michael addition reactions [11].

SCHEME 5.11 Conversion of carboxylic acids into sulfones [12].

SCHEME 5.12 Ring opening of epoxides with thiolate anions [13].

SCHEME 5.13 Imidazoline-phosphoric acid-catalyzed opening of aziridines [14].

SCHEME 5.14 Synthesis of dithioacetals from alkynes [15].

SCHEME 5.15 Decarboxylative thiolation of alkyl carboxylic acids [16].

SCHEME 5.16 Rhodium-catalyzed synthesis of allylic sulfones [17].

SCHEME 5.17 Synthesis of

gem

-dithioacetates through substitution chemistry [18].

SCHEME 5.18 Enantioselective synthesis of sulfoxides using a chiral organocatalyst [19].

SCHEME 5.19 Synthesis of β-keto aryl sulfones using a nongaseous source of SO

2

[20].

SCHEME 5.20 Nucleophilic substitution chemistry with sodium phenylsulfinate [21].

SCHEME 5.21 Palladium-catalyzed synthesis of alkyl aryl sulfides [30].

SCHEME 5.22 Palladium-catalyzed synthesis of diaryl sulfides [34].

SCHEME 5.23 Synthesis of phenothiazine derivatives based upon a three-component coupling reaction [37].

SCHEME 5.24 Palladium-catalyzed synthesis of crowded diaryl sulfides [38].

SCHEME 5.25 Preparation of diaryl sulfides from aryl benzyl sulfides.

SCHEME 5.26 Palladium-catalyzed CH thiolation of arenes [41].

SCHEME 5.27 Copper-catalyzed diaryl sulfide synthesis [43].

SCHEME 5.28 CuI/neocuproine-catalyzed synthesis of diaryl sulfides [44].

SCHEME 5.29 Diaryl sulfide synthesis using CS

2

as the sulfur source [45].

SCHEME 5.30 Heterocycle synthesis using CS

2

as the sulfur source [45].

SCHEME 5.31 Nickel-catalyzed synthesis of unsymmetrical diaryl sulfides [47].

SCHEME 5.32 Rhodium-catalyzed coupling of aryl chlorides with thiols [53].

SCHEME 5.33 Synthesis of thioesters in water [54].

SCHEME 5.34 Coupling of arenes with diphenyl disulfide [55].

SCHEME 5.35 CH thiolation of heterocycles [56].

SCHEME 5.36 CH sulfenylation of heterocycles [57].

SCHEME 5.37 Synthesis of unsymmetrical diorganosulfides through sulfenylchloride intermediates [59].

SCHEME 5.38 Transition metal-free synthesis of unsymmetrical diaryl sulfides [60].

SCHEME 5.39 Synthesis of phenothiazine derivatives [61].

SCHEME 5.40 A three-component reaction leading to benzothiazoles [62].

SCHEME 5.41 Benzothiazole synthesis through CH functionalization [63].

SCHEME 5.42 Preparation of 2-aminothiazoles [64].

SCHEME 5.43 Synthesis of functionalized benzothiophenes through iodocyclization [65].

SCHEME 5.44 CH thiolation of pyrazolones to afford aryl pyrazolone thioethers [66].

SCHEME 5.45 Ruthenium-catalyzed synthesis of diaryl sulfones [67].

SCHEME 5.46 Palladium-catalyzed ortho-sulfonation of 2-phenylpyridine [68].

SCHEME 5.47 Palladium-catalyzed synthesis of diaryl sulfones [69].

SCHEME 5.48 Transition metal-free synthesis of diaryl sulfones [70].

SCHEME 5.49 Synthesis of vinyl sulfides through copper-catalyzed cross-coupling [72].

SCHEME 5.50 Preparation of vinyl sulfides using a copper catalyst generated in situ [73].

SCHEME 5.51 Conversion of 1,1-dibromoalkenes into vinyl sulfides [75].

SCHEME 5.52 Vinyl sulfide synthesis through decarboxylation of carboxylic acids [76].

SCHEME 5.53

E

-selective palladium-catalyzed hydrothiolation of alkynes [79].

SCHEME 5.54 Hydrothiolation of alkynylphosphines [80].

SCHEME 5.55 Nickel-catalyzed hydrothiolation of alkynes [81].

SCHEME 5.56 Rhodium-catalyzed hydrothiolation of alkynes [82].

SCHEME 5.57 Addition of thiols to alkynes using an NHC-ligated rhodium catalyst [85].

SCHEME 5.58 Overall Z-selective hydrothiolation of internal and terminal alkynes [88].

SCHEME 5.59 Hydrothiolation of 3-aryl-2-propynenitriles [89].

SCHEME 5.60 Preparation of vinyl sulfones through a copper-promoted decarboxylation reaction [90].

SCHEME 5.61 Decarboxylative synthesis of vinyl sulfones [92].

SCHEME 5.62 Conversion of cinnamic acid derivatives into sulfonated benzofurans [94].

SCHEME 5.63 Preparation of vinyl sulfones through palladium-catalyzed cross-coupling [69].

SCHEME 5.64 Iridium-catalyzed preparation of vinyl sulfones [96].

SCHEME 5.65 Conversion of terminal alkynes into alkynyl sulfides [101].

SCHEME 5.66 Conversion of thiophenols into alkynyl aryl sulfides [103].

SCHEME 5.67 Trifluoromethylthiolation of alkynes in air [106].

SCHEME 5.68 Synthesis of alkynyl sulfides from sulfonamides [107].

Chapter 06

SCHEME 6.1 Alkylboronate synthesis through the treatment of pinacolborane with Grignard reagents [2].

SCHEME 6.2 Synthesis of allylborane [2].

SCHEME 6.3 Metal-free borylation of alkyl halides [3].

SCHEME 6.4 Copper-catalyzed borylation of alkyl halides [4].

SCHEME 6.5 Zinc-catalyzed conversion of alkyl halides into alkylboronates [11].

SCHEME 6.6 Platinum-catalyzed borylation of activated alkenes [12, 13].

SCHEME 6.7 Copper-catalyzed borylation of functionalized cyclopropenes [15].

SCHEME 6.8 Asymmetric borylation of unactivated cyclopropenes [16].

SCHEME 6.9 Iron-catalyzed hydroboration of conjugated dienes [23].

SCHEME 6.10 Iron-catalyzed synthesis of allylboronates [22].

SCHEME 6.11 Palladium-catalyzed borylation of allylic chlorides [24].

SCHEME 6.12 Nickel-catalyzed borylation of allylic acetates [24].

SCHEME 6.13 Synthesis and rearrangement of allylboronates [25].

SCHEME 6.14 One-pot synthesis of allylboronates [2].

SCHEME 6.15 Cobalt-catalyzed asymmetric synthesis of alkylboronates [27].

SCHEME 6.16 Synthesis of alkyl MIDA boronates [29].

SCHEME 6.17 Rhodium-catalyzed preparation of alkylboronates from alkylnitriles [31].

SCHEME 6.18 LDA-promoted boronate rearrangement reaction [32].

SCHEME 6.19 Application of arylboroxines to the synthesis of alkylboronates [33].

SCHEME 6.20 Synthesis of arylboronic acids using an I/MgBr exchange reaction [41].

SCHEME 6.21 Chemoselective metalation/borylation [45].

SCHEME 6.22 One-pot approach to the synthesis of arylboronates using elemental magnesium [2].

SCHEME 6.23 Borylation of

N

-methyl-4-bromooxindole [46].

SCHEME 6.24 Palladium-catalyzed coupling of B

2

pin

2

with aryl halides [47].

SCHEME 6.25 Palladium-catalyzed coupling of bulky aryl halides with B

2

pin

2

[48].

SCHEME 6.26 Palladium-catalyzed synthesis of arylboronates [49].

SCHEME 6.27 Palladium-catalyzed synthesis of arylboronates using pinacolborane [51].

SCHEME 6.28 Palladium-catalyzed route to valuable boron reagents [56].

SCHEME 6.29 Zinc-catalyzed synthesis of arylboronates [61].

SCHEME 6.30 Conversion of arylnitriles into arylboronates [31].

SCHEME 6.31 Rhodium-catalyzed borylation through CO bond cleavage [62].

SCHEME 6.32 Metal-free deaminoborylation of arylamines [63].

SCHEME 6.33 Metal-free synthesis of arylboronates [3].

SCHEME 6.34 Iridium-catalyzed CH borylation of indoles [75].

SCHEME 6.35 Preparation of diphenylborinic acid [76].

SCHEME 6.36 Palladium-catalyzed synthesis of vinylboronates from vinyl triflates [77].

SCHEME 6.37 Palladium-catalyzed coupling of vinyl halides with pinacolborane [51].

SCHEME 6.38 Zinc-catalyzed borylation of bromostyrene [61].

SCHEME 6.39 Addition of B–Br bonds to alkynes and conversion into a vinylboronate [81].

SCHEME 6.40 Synthesis of vinylboronates through cleavage of C–C bonds [31].

SCHEME 6.41 Metal-free synthesis of a vinylboronate [3].

SCHEME 6.42 Ruthenium-catalyzed preparation of

Z

-vinylboronates [82].

SCHEME 6.43 Stereoselective synthesis of

Z

-vinylboronates using hydroboration/protodeboronation [83].

SCHEME 6.44 Preparation of chlorinated vinylboronate compounds [84].

SCHEME 6.45 Hydroboration of terminal alkynes using Schwartz’s reagent as the catalyst [85].

SCHEME 6.46 Palladium-catalyzed silylborylation of alkynylboronates [86].

SCHEME 6.47 Gold-catalyzed addition of B

2

pin

2

to alkynes [87].

SCHEME 6.48 Addition of pinacolborane to alkynes catalyzed by carboxylic acids [91].

SCHEME 6.49 Borylation of internal alkynes [92].

SCHEME 6.50 Synthesis of allenylboronates [93].

SCHEME 6.51 Copper-catalyzed borylation of allenes [95].

SCHEME 6.52 Synthesis of alkynylboronates using an organolithium approach [84].

SCHEME 6.53 Synthesis of alkynyltrifluoroborate salts [104].

SCHEME 6.54 Iridium-catalyzed synthesis of alkynylboronates [107].

SCHEME 6.55 Zinc-catalyzed coupling of terminal alkynes with 1,8-naphthalenediaminatoborane [108].

Chapter 07

SCHEME 7.1 Copper-catalyzed fluorination of alkyl triflates [8].

SCHEME 7.2 Zinc-catalyzed asymmetric fluorination of malonates [9].

SCHEME 7.3 Transition metal-free fluorination of methyl ketones [10].

SCHEME 7.4 Copper-catalyzed fluorination of allylic bromides [11].

SCHEME 7.5 Photocatalyzed benzyl CH fluorination [13].

SCHEME 7.6 Photocatalyzed benzyl CH fluorination under continuous flow [14].

SCHEME 7.7 Fluorination of CH bonds [15].

SCHEME 7.8 Radical benzyl CH fluorination using triethylborane [16].

SCHEME 7.9 Asymmetric benzyl CH fluorination using titanium alkoxide [17].

SCHEME 7.10 Enantioselective synthesis of allylic fluorides [20].

SCHEME 7.11 Fluorination using BF

3

etherate as F source [22].

SCHEME 7.12 Light-promoted fluorination of CH bonds [25].

SCHEME 7.13 Palladium-catalyzed fluoroarylation of styrene derivatives [26].

SCHEME 7.14 Cobalt-catalyzed hydrofluorination of unactivated alkenes [28].

SCHEME 7.15 Transition metal-free oxyfluorination of styrene derivatives [29].

SCHEME 7.16 Bromination of MIDA boronates [30].

SCHEME 7.17 One-pot chlorination/reduction of resolved citronellal [31].

SCHEME 7.18 Fluorinative stereodivergent semipinacol rearrangement [32].

SCHEME 7.19 Asymmetric semipinacol rearrangement using a DHQD-based organocatalyst [33].

SCHEME 7.20 Asymmetric bromination–semipinacol rearrangement [34].

SCHEME 7.21 Silver-promoted fluorination of alkylboronates using Selectfluor [27].

SCHEME 7.22 Copper-catalyzed aminofluorination of styrene derivatives [35].

SCHEME 7.23 Silver-catalyzed decarboxylative fluorination [36].

SCHEME 7.24 Conversion of alcohols into alkyl iodides using Appel-type chemistry [38].

SCHEME 7.25 Selective monochlorination of diols using TCT [42].

SCHEME 7.26 Conversion of alcohols into alkyl halides [43].

SCHEME 7.27 Triphenylphosphine oxide-catalyzed Appel reaction [44].

SCHEME 7.28 Synthesis of alkyl chlorides by chlorodecarboxylation [49].

SCHEME 7.29 Reductive bromination of carboxylic acids [50].

SCHEME 7.30 Reductive chlorination of carboxylic acids using GaCl

3

[52].

SCHEME 7.31 Using alkyl mesylates in Finkelstein reactions [54].

SCHEME 7.32 Enantioselective chlorination of keto esters [55].

SCHEME 7.33 Organocatalyzed iodoaminocyclization of hydrazones [56].

SCHEME 7.34 Asymmetric bromocyclization using a DABCO-bromine adduct [57].

SCHEME 7.35 Enantioselective bromocyclization of styrenyl carboxylic acids [58].

SCHEME 7.36 Bromocyclization in air [59].

SCHEME 7.37 Asymmetric phosphoramidate synthesis through iodocyclization [60].

SCHEME 7.38 Kinetic resolution through organocatalyzed chlorocyclization [61].

SCHEME 7.39 Gold-catalyzed regioselective double addition of HF to alkynes [63].

SCHEME 7.40 Gold-catalyzed conversion of propargyl alcohols into diiodo-β-hydroxyketones [64].

SCHEME 7.41 Conversion of benzaldehyde into dibromotoluene [65].

SCHEME 7.42 Chloroformyloxylation of alkenes [67].

SCHEME 7.43 Direct α-chlorination of alkenes [67].

SCHEME 7.44 Conversion of alcohols to chloroaldehydes and ketones [68].

SCHEME 7.45 Chlorination of a propargyl alcohol [64].

SCHEME 7.46 Synthesis of functionalized aryl fluorides by treatment of aryl Grignard reagents with NFSI [80].

SCHEME 7.47 Synthesis of aryl fluorides by treatment of aryl Grignard reagents with F

+

[79].

SCHEME 7.48 Fluorination of arylstannanes [82, 83].

SCHEME 7.49 Copper-promoted fluorination of arylstannanes [84].

SCHEME 7.50 Palladium-catalyzed fluorination of aryl triflates using CsF [85].

SCHEME 7.51 Palladium-catalyzed fluorination of aryl triflates under continuous flow [88].

SCHEME 7.52 Palladium-catalyzed conversion of heteroaryl bromides into heteroaryl fluorides [89].

SCHEME 7.53 Copper-catalyzed conversion of aryl bromides into aryl fluorides [90].

SCHEME 7.54 Fluorination of aryltrialkoxysilanes using Selectfluor [91].

SCHEME 7.55 Silver-mediated fluorination of arylboronic acids [92].

SCHEME 7.56 Copper-promoted conversion of arylboronates into aryl fluorides [93].

SCHEME 7.57 Fluorination of aryltrifluoroborate salts using KF [94].

SCHEME 7.58 Copper-promoted fluorination of aryltrifluoroborate salts [84].

SCHEME 7.59 Copper-promoted fluorination of diaryliodonium salts [96].

SCHEME 7.60 Deoxyfluorination of phenols [98].

SCHEME 7.61 Microwave-assisted fluorination [12].

SCHEME 7.62 Palladium-catalyzed NMP-promoted fluorination of CH bonds [100].

SCHEME 7.63 Quinoxaline-directed fluorination of CH bonds [101].

SCHEME 7.64 Nitrate-promoted palladium-catalyzed CH fluorination using

O

-methyl oxime ethers as directing groups [102].

SCHEME 7.65 Palladium-catalyzed ortho-directed fluorination of

N

-phenylbenzamide derivatives [107].

SCHEME 7.66 Palladium-catalyzed ortho-directed fluorination using NFSI [108].

SCHEME 7.67 Bromination of a CH bond using elemental bromine [114].

SCHEME 7.68 Iodination of arenes using KI/TBHP [119].

SCHEME 7.69 Halogen exchange using BuLi/X

2

[120].

SCHEME 7.70 Halogen exchange using a metallation/halogenation approach [121].

SCHEME 7.71 Bromination of deactivated arenes [123].

SCHEME 7.72 Bromination of deactivated arenes using NBS in sulfuric acid [124].

SCHEME 7.73 Bromination of purine derivatives using pyridinium bromide [125].

SCHEME 7.74 Halogenation of electron-deficient arenes [126].

SCHEME 7.75 Copper-promoted chlorodeboronation reactions [127].

SCHEME 7.76 Chlorodeboronation of electron-rich aryltrifluoroborates [128].

SCHEME 7.77 Metal-free halodeboronation reactions [130].

SCHEME 7.78 Iododeboronation of arylboronic acids using NIS generated in solution [130].

SCHEME 7.79 Conversion arenes into aryl iodides using a borylation/iodination approach [132].

SCHEME 7.80 Gold-catalyzed halogenation of arylboronate esters [133].

SCHEME 7.81 Palladium-catalyzed ortho-directed halogenation of arylnitriles [139].

SCHEME 7.82 Palladium-catalyzed halogenation of aminotetrazoles [140].

SCHEME 7.83 A competition experiment to probe the directing ability of various functional groups [141].

FIGURE 7.1 A general order of directing ability for different groups [141].

SCHEME 7.84 Rhodium-catalyzed halogenation of tertiary benzamides [143].

SCHEME 7.85 Cobalt-catalyzed ortho-halogenation of benzamides [144].

SCHEME 7.86 A copper-catalyzed aromatic Finkelstein reaction [146].

SCHEME 7.87 An aromatic Finkelstein reaction under continuous flow [147].

SCHEME 7.88 Nickel-catalyzed aromatic Finkelstein reaction [148].

SCHEME 7.89 Palladium-catalyzed double iodination of benzoic acid [149].

SCHEME 7.90 Palladium-catalyzed monoiodination of benzoic acid derivatives [149].

SCHEME 7.91 Palladium-catalyzed halogenation of aryl triflates [150].

SCHEME 7.92 Ruthenium-catalyzed halogenation of aryl triflates [151].

SCHEME 7.93 Palladium-catalyzed iodination using elemental iodine [152].

SCHEME 7.94 Synthesis of 1,2-diiodo arenes by trapping benzynes with I

2

[153].

SCHEME 7.95 Palladium-catalyzed asymmetric synthesis of aryl iodides [154].

SCHEME 7.96 Iodination of a borane using NIS [155].

SCHEME 7.97 Use of a silicon-based directing group in a palladium-catalyzed iodination reaction [156].

SCHEME 7.98 Synthesis of unsymmetrical diaryliodonium triflates [160, 161].

SCHEME 7.99 Synthesis of bulky symmetrical diaryliodonium triflates [160, 161].

SCHEME 7.100 Synthesis of diaryliodonium salts from arylboronic acids [162].

SCHEME 7.101 Synthesis of vinyl fluorides from vinylboronic acids [92].

SCHEME 7.102 Palladium-catalyzed addition fluorination of CH bonds [102].

SCHEME 7.103 Gold-catalyzed hydrofluorination of terminal alkynes [63].

SCHEME 7.104

gem

-Difluoroolefination of aldehydes [167].

SCHEME 7.105 Conversion of diazo compounds into

gem

-difluoroalkenes [168].

SCHEME 7.106 Acyl fluoride synthesis from aryl bromides [171].

SCHEME 7.107 Triethylamine-catalyzed Hunsdiecker decarboxylative halogenation [172].

SCHEME 7.108 Palladium-catalyzed conversion of vinyl triflates into vinyl halides [150].

SCHEME 7.109 Ruthenium-catalyzed conversion of vinyl triflates into vinyl bromides [151].

SCHEME 7.110 Conversion of vinyltrifluoroborate salts into vinyl bromides [129].

SCHEME 7.111 Conversion of vinyltrifluoroborates into vinyl chlorides [128].

SCHEME 7.112 Synthesis of vinyl iodides and bromides based upon initial bromoboration of an alkyne [177].

SCHEME 7.113 Rhodium-catalyzed halogenation of vinylamides [178].

SCHEME 7.114 Conversion of allylic alcohols to halogenated vinyl ketones [179].

SCHEME 7.115 Cobalt-catalyzed iodination of Michael acceptors [144].

SCHEME 7.116 Bromination of a dichloroquinone derivative using pyridinium tribromide [180].

SCHEME 7.117 Formal hydroiodination of alkyne using the I

2

/HP(O)Ph

2

system [181].

SCHEME 7.118 α-Chlorination of activated alkenes using iodobenzene dichloride [67].

SCHEME 7.119 Preparation of vinyl iodides and bromides from propargyl alcohols [183].

SCHEME 7.120 α-Bromination of activated alkenes [174].

SCHEME 7.121 Nickel-catalyzed α-selective formal hydrobromination of alkynes [184].

SCHEME 7.122 Nickel-catalyzed β-selective formal hydrobromination of alkynes [184].

SCHEME 7.123 Silver-promoted synthesis of β-haloenol acetates [185].

SCHEME 7.124 Titanium-mediated synthesis of vinyl bromides and chlorides [187].

SCHEME 7.125 Ruthenium-catalyzed halogenation of unfunctionalized styrenes [188].

SCHEME 7.126 Iodocyclization of substituted ynamides [190].

SCHEME 7.127 NIS-promoted synthesis of dihydrooxazoles in DMF [191].

SCHEME 7.128 NIS-promoted synthesis of oxazolidine in dichloromethane [191].

SCHEME 7.129 Eelectrophilic cyclization of diynes [38].

SCHEME 7.130 Iodocyclization of propargyl alcohols [192].

SCHEME 7.131 Synthesis of 3-iodofurans through iodocyclization [193].

SCHEME 7.132 Synthesis of 3-iodothiofurans through iodocyclization [194].

SCHEME 7.133 Palladium-catalyzed synthesis of vinyl chlorides [195].

SCHEME 7.134 Brominative cyclization of a diyne [196].

SCHEME 7.135 Asymmetric synthesis of vinyl iodides through iodolactonization [197].

SCHEME 7.136 Copper-promoted synthesis of vinyl bromides through cyclization [198].

SCHEME 7.137 Gold-catalyzed synthesis of heterocycles [199].

SCHEME 7.138 Cyclization of allenoates using aluminum chloride [200].

SCHEME 7.139 Conversion of aldehydes into vinyl bromides [203].

SCHEME 7.140 Regioselective conversion of tosylhydrazones into vinyl halides [204].

SCHEME 7.141 Chlorodeamination of heterocycles [205].

SCHEME 7.142 Synthesis of halogenated glycals [206].

SCHEME 7.143 Synthesis of halogenated styrenes from benzyl halides [207].

SCHEME 7.144 Dehydrogenative aminohalogenation of alkenes [208].

SCHEME 7.145 Synthesis of dibromoalkenes through a Wittig-type approach [212].

SCHEME 7.146 Synthesis of

gem

-diiodoalkene from aldehydes [214].

SCHEME 7.147 Regio- and stereoselective dibromination of alkynes [217].

SCHEME 7.148 Solvent- and catalyst-free halogenation of phenylacetylene derivatives [219].

SCHEME 7.149 Regio- and stereoselective synthesis of

Z

-1-iodo-2-bromoalkenes [220].

SCHEME 7.150 Generation and use of acyl chlorides in solution [221].

SCHEME 7.151 Synthesis of alkynyl chlorides using

N

-chlorophthalimide [240].

SCHEME 7.152 Dependence of the chlorination reaction on TBAF [242].

SCHEME 7.153 Hunsdiecker synthesis of bromoalkynes using TBAFTFA/NBS [246].

SCHEME 7.154 Triethylamine-promoted Hunsdiecker synthesis of bromoalkynes [172].

SCHEME 7.155 Preparation of bromoalkynes using the NBS/AgNO

3

[241].

SCHEME 7.156 Gold-catalyzed bromination of terminal alkynes [252].

SCHEME 7.157 Desilylation/bromination using AgF [253].

SCHEME 7.158 Conversion of alkynyltrifluoroborate salts into alkynyl bromides [129].

SCHEME 7.159 Iodination of ynamides using KHMDS/I

2

[260].

SCHEME 7.160 Iodination of ynamides using BuLi/I

2

[260].

SCHEME 7.161 Synthesis of iodoalkynes using TBATFA-promoted decarboxylation [246].

SCHEME 7.162 Synthesis of iodoalkynes using potassium iodide as the halogen source [119].

SCHEME 7.163 Synthesis of iodoalkynes using AgNO

3

/NIS [241].

SCHEME 7.164 Synthesis of haloalkynes using DBU/NXS combinations [240].

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