Metal catalyzed cross coupling reactions and more  volume 1

1.3.1 Reductive Elimination to Generate C–N, C–O, and C–S Bonds fromOrganopalladiumII Complexes 39 1.3.2 Nickel- and Copper-Catalyzed Formation of C–X Bonds 44 1.4 Summary and Outlook 46

Trang 3

Armin de Meijere, Stefan Br¨ase, and Martin Oestreich

Metal-Catalyzed Cross-Coupling Reactions and More

Trang 4

Szab´o, K.J., Wendt, O.F (eds.)

Pincer and Pincer-Type

Burke, A.J., Silva Marques, C

Catalytic Arylation Methods

From the Academic Lab to Industrial

Practical Aspects and Future Developments

2013 Print ISBN: 978-3-527-33254-0; also available in electronic formats

Magano, J., Dunetz, J.R (eds.)

Transition Metal-Catalyzed Couplings in Process ChemistryCase Studies from the Pharmaceutical Industry

Ackermann, L (ed.)

Modern Arylation Methods

Trang 5

Martin Oestreich

Metal-Catalyzed Cross-Coupling Reactions and More

Volume 1

Trang 6

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Trang 7

Contents to Volume 1

Preface XV

List of Contributors XVII

1 Mechanistic Aspects of Metal-Catalyzed C,C- and C,X-Bond Forming

Reactions 1

Antonio M Echavarren and Anna Homs

1.1 Mechanisms of Cross-Coupling Reactions 1

1.1.1 The Earlier Mechanistic Proposal: The Stille Reaction 2

1.1.2 The Oxidative Addition 3

1.1.2.1 Cis-Complexes in the Oxidative Addition 4

1.1.2.2 The Role of Alkene and Anionic Ligands 5

1.1.2.3 Cross-Couplings in the Presence of Bulky Phosphines 6

1.1.2.4 N-Heterocyclic Carbenes as Ligands 12

1.1.2.5 Palladacycles as Catalysts 13

1.1.2.6 Involvement of Pd(IV) in Catalytic Cycles 14

1.1.2.7 Oxidative Addition of Stannanes to Pd(0) 16

1.1.3 The Transmetallation in the Stille Reaction 16

1.1.3.1 Isolation of the Transmetallation Step 16

1.1.3.2 Dissociative Mechanistic Proposals 18

1.1.3.3 Cyclic and Open Associative Transmetallation 19

1.1.3.4 The Copper Effect 23

1.1.3.5 Transmetallation in the Suzuki–Miyaura Reaction 24

1.1.3.6 Transmetallation in the Negishi Reaction 27

1.1.3.7 Transmetallation in the Hiyama Reaction 28

1.1.3.8 Couplings Catalyzed by Copper and Gold 30

1.1.3.9 Couplings Catalyzed by Iron and Cobalt 32

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1.3.1 Reductive Elimination to Generate C–N, C–O, and C–S Bonds from

Organopalladium(II) Complexes 39

1.3.2 Nickel- and Copper-Catalyzed Formation of C–X Bonds 44

1.4 Summary and Outlook 46

List of Abbreviations 46

References 47

2 State-of-the-Art in Metal-Catalyzed Cross-Coupling Reactions of

Organoboron Compounds with Organic Electrophiles 65

Jack C.H Lee and Dennis G Hall

2.1 Introduction 66

2.1.1 Catalytic Cycle 66

2.1.2 Improvements toward More Efﬁcient Cross-Coupling Conditions 69

2.1.2.1 Development of New Phosphine and NHC Ligands 69

2.1.2.2 Usage of Masked Boron Derivatives as Cross-Coupling Partners 70

2.1.2.3 Lewis Acids as Additives 72

2.1.2.4 Adjusting the Nucleophilicity of Organoboron Cross-Coupling

Partners 73

2.1.2.5 Copper Salts as Additives 74

2.2 Advances in Cross-Coupling Reactions for the Formation of

2.2.3.2 N-Methyliminodiacetic Acid (MIDA) Boronates 97

2.2.3.3 Other Organoboron Cross-Coupling Partners 99

2.2.4 Synthesis of Enantiomerically Enriched Atropisomers 101

2.3 Advances in the Cross-Coupling Reactions for the Formation of

Trang 9

2.3.3.2 Stereoselective Cross-Coupling Reactions of sp3Alkyl Halides with sp3

2.4.5 1-Phenyl-1-(4-acetylphenyl-ethane (ArI= 4-iodoacetophenone) 122

2.4.6 Naphthalene-1,8-diamido (dan) derivative (Ar= Ph) 123

2.4.7 2-Methyl-5-phenylpentyl benzyl(phenyl)carbamate (Ralkyl= Me,

X= Br, Ralkyl= CH2CH2CH2Ph) 123

2.5 Summary and Outlook 124

References 124

3 Pd-Catalyzed Cross-Coupling with Organometals Containing Zn, Al, Zr,

and so on – The Negishi Coupling and Its Recent Advances 133

Shiqing Xu, Hirofumi Kamada, Eun Hoo Kim, Akimichi Oda, and

Ei-ichi Negishi

3.1 Background and Discovery 134

3.1.1 Why Metals? Why Transition Metals? 134

3.1.2 Why Transition Metal-Catalyzed Organometallic Reactions? 136

3.2 Discovery of the Pd- or Ni-Catalyzed Cross-Coupling Reactions of

Organometals Containing Zn, Al, Zr, and B 137

3.3 The Current Scope of the Pd- or Ni-Catalyzed Cross-coupling and Its

Application to the Synthesis of Natural Products and Other ComplexOrganic Compounds 154

3.3.1 Cross-Coupling between Two Unsaturated (Aryl, Alkenyl, and/or

3.3.2 Cross-Coupling Involving One Allyl, Benzyl, or Propargyl Group 197

3.3.2.1 1,4-Dienes via Pd-Catalyzed Alkenyl–Allyl and Allyl–Alkenyl Coupling

and 1,4-Enynes by Pd-Catalyzed Alkynyl–Allyl Coupling 197

3.3.2.2 Benzyl–Aryl, Aryl–Benzyl Coupling 203

3.3.2.3 Allylbenzene Derivatives via Pd-Catalyzed Alkenyl–Benzyl Coupling

and Aryl–Allyl and Allyl–Aryl Coupling 204

3.3.2.4 Benzylated Alkynes via Pd-Catalyzed Alkynyl–Benzyl Coupling and

Aryl–Propargyl as well as Propargyl–Aryl Coupling 204

3.3.2.5 1,4-Diynes via Alkynyl–Propargyl Coupling 207

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3.3.2.6 Synthesis of Natural Products Containing 1,4-Diene and Allylated

Arenes by Pd-Catalyzed Allylation, Benzylation, and

Propargylation 208

3.3.3 Cross-Coupling between Two Allyl, Benzyl, and/or Propargyl

Groups 210

3.3.3.1 1,5-Dienes and 1,5-Enynes via Pd-Catalyzed Cross-Couplings with

Allyl, Benzyl, Propargyl Electrophiles 210

3.3.3.2 1,5-Dienes and 1,5-Enynes via Pd-Catalyzed Homoallyl–Alkenyl

Coupling and Homopropargyl–Alkenyl Coupling 212

3.3.3.3 Bibenzyls, Homoallylarenes, 1,5-Dienes, Homopropargylarenes, and

1,5-Enynes via Pd-Catalyzed Negishi Coupling 214

3.3.4 Cross-Coupling Involving Alkylmetals and/or Alkyl Electrophiles

Other Than Those Containing Allyl, Benzyl, and/or PropargylGroups 216

3.3.4.1 Pd-Catalyzed Alkyl–Alkyl Coupling 219

3.3.4.2 Ni-Catalyzed Alkyl–Alkyl Coupling 221

3.3.4.3 Catalytic Asymmetric Cross-Coupling Reactions with Secondary Alkyl

3.3.5.3 Pd-Catalyzedα-Substitution of Enolates and Related Derivatives 233

3.4 Zr-Catalyzed Asymmetric Carboalumination of Alkenes (ZACA)

ZACA–Pd- or Cu-Catalyzed Cross-Coupling Sequential Processes as aGeneral Route to Enantiomerically Enriched Chiral Organic

Compounds 243

3.4.1 Zirconium-Catalyzed Asymmetric Carboalumination of Alkenes

(ZACA Reaction) 243

3.4.1.1 Historical and Mechanistic Background of Carbometallation of

Alkenes and Alkynes with Alkylzirconocene Derivatives 244

3.4.1.2 Catalytic Asymmetric Carbometallation of Alkenes Proceeding via

Dzhemilev Ethylmagnesiations 246

3.4.2 Current Summary of Development and Application of the ZACA

Reaction and Conclusion 249

3.4.2.1 ZACA–Pd-Catalyzed Cross-Coupling Sequential Processes for the

Synthesis of Deoxypolypropionates and Related Compounds 249

3.4.2.2 ZACA–Lipase-Catalyzed Acetylation–Pd- or Cu-Catalyzed

Cross-Coupling Synergy to Chiral Organic Compounds 253

3.5 Representative Experimental Procedures 260

Trang 11

4.2 Methods of Preparation of Zinc Organometallics 280

4.2.1 Direct Insertion of Zn(0) into Organohalides 280

4.2.2 Transmetallation Reactions 282

4.2.2.1 Transmetallation Reactions with Main-Group and Transition Metal

Organometallics 282

4.2.2.2 Boron–Zinc Exchange Reactions 285

4.2.3 Direct Zincation Reactions 287

4.2.4 Halogen–Zinc Exchange Reactions 288

4.2.5 Hydro- and Carbozincation Reactions 290

4.3 Uncatalyzed Cross-Coupling Reactions of Organozinc Reagents 291

4.4 Copper-Catalyzed Cross-Coupling Reactions of Organozinc

Reagents 293

4.4.1 Cross-Coupling with C(sp)- or C(sp2)-Electrophiles 293

4.4.2 Cross-Coupling Reactions with C(sp3)-Electrophiles 295

4.5 Transition-Metal-Catalyzed Cross-Coupling Reactions of Organozinc

Reagents 296

4.5.1 Cross-Coupling Reactions of C(sp2)-Organozinc Reagents 297

4.5.1.1 Palladium-Catalyzed Cross-Coupling Reactions 297

4.5.1.2 Nickel-Catalyzed Cross-Coupling Reactions 311

4.5.1.3 Rhodium-Catalyzed Cross-Coupling Reactions 315

4.5.1.4 Cobalt-Catalyzed Cross-Coupling Reactions 316

4.5.1.5 Iron-Catalyzed Cross-Coupling Reactions 317

4.5.2 Cross-Coupling Reactions of Alkynylzinc Reagents 318

4.5.2.1 Cross-Coupling with C(sp2)-Electrophiles 318

4.5.2.2 Cross-Coupling with C(sp3)-Electrophiles 320

4.5.3 Cross-Coupling Reactions of C(sp3)-Organozinc Reagents 321

Trang 12

4.5.3.3 Platinum-Catalyzed Cross-Coupling Reactions 342

5.2 Methods of Preparation of Magnesium Organometallics 366

5.2.1 Direct Insertion of Magnesium 366

Trang 13

5.2.2 Halogen–Magnesium Exchange Reactions 366

5.2.3 Direct Magnesiation Reactions 368

5.3 Transition-Metal-Catalyzed Cross-Coupling Reactions of

Organomagnesium Reagents 370

5.3.1 Cross-Coupling of C(sp2)-Organomagnesium Reagents 372

5.3.1.5 Manganese-Catalyzed Cross-Coupling Reactions 383

5.3.2 Cross-Coupling Reactions of C(sp)-Organomagnesium

Reagents 384

5.3.2.3 Manganese-Catalyzed Oxidative Cross-Coupling Reactions 388

5.3.3 Cross-Coupling Reactions of C(sp3)-Organomagnesium

Reagents 390

5.3.3.4 Copper-Catalyzed Cross-Coupling Reactions 406

5.3.3.5 Cobalt-Catalyzed Reactions 408

5.3.3.6 Manganese-Catalyzed Cross-Coupling Reactions 410

5.3.3.7 Silver-Catalyzed Cross-Coupling Reactions 410

Trang 14

6 Organotin Reagents in Cross-Coupling Reactions 423

Belén Mart´ın-Matute, Kálmán J Szabó, and Terence N Mitchell

6.2.2.2 New Ligands, Catalysts, and Additives 429

6.2.2.3 New Organic and Organotin Coupling Partners 434

6.2.2.4 Polymer-Supported Stille Chemistry 435

6.2.2.5 Other Advances in Methodology 436

6.3 Natural Product Synthesis 443

6.3.1 Intramolecular Couplings 444

6.3.2 Intermolecular Couplings 446

6.3.2.1 Vinyl–Vinyl Couplings 446

6.3.2.2 Other Couplings Involving Vinyltins 448

6.3.2.3 Couplings of Heterocyclic Organotins 449

6.3.2.4 Other Intermolecular Couplings 449

6.5.3 Materials Based on Pyrrole and Furan 460

6.5.4 Polyphenylenevinylene and Related Materials 460

Trang 15

List of Abbreviations 465

References 465

List of Contributors XIII

7 Organosilicon Compounds in Cross-Coupling Reactions 475

Scott E Denmark and Ramzi F Sweis

8 Cross-Coupling of Organyl Halides with Alkenes – The Heck

Reaction 533

Stefan Br¨ase and Armin de Meijere

9 Cross-Coupling Reactions to sp Carbon Atoms 665

Tobias A Schaub and Milan Kivala

10 Carbometallation Reactions 763

Ilan Marek and Yury Minko

11 Palladium-Catalyzed 1,4-Additions to Conjugated Dienes 875

Jan-Erling B¨ackvall

12 Cross-Coupling Reactions viaπ-Allylmetal Intermediates 925

Anton Bayer and Uli Kazmaier

13 Palladium-Catalyzed Aromatic Carbon–Nitrogen Bond Formation 995

Jan Paradies

14 The Directed Ortho Metallation (DoM)–Cross-Coupling Nexus.

Synthetic Methodology for the Formation of Aryl–Aryl and

Aryl–Heteroatom–Aryl Bonds 1067

Victor Snieckus and Eric J.-G Anctil

15 Transition-Metal-Catalyzed Hydroamination Reactions 1135

Laurel L Schafer, Jacky C.-H Yim, and Neal Yonson

16 Oxidative Functionalization of Alkenes 1259

Kilian Mu˜ niz and Claudio Mart´ınez

Trang 16

17 Biaryl Synthesis through Metal-Catalyzed C–H Arylation 1315

Junichiro Yamaguchi and Kenichiro Itami

Tetsuya Satoh and Masahiro Miura

19 C–H Bond Alkylation (Including Hydroarylation of Alkenes) 1427

Ludivine Jean-G´erard, Rodolphe Jazzar, and Olivier Baudoin

Index 1495

Trang 17

Preface XV

Reactions 1

Shiqing Xu, Hirofumi Kamada, Eun Hoo Kim, Akimichi Oda,

and Ei-ichi Negishi

4 Carbon–Carbon Bond Forming Reactions Mediated by Organozinc

Trang 18

7.1 Introduction 475

7.1.1 Background of Silicon-Based Cross-Coupling Reactions 475

7.1.2 Discovery and Early Development Work 476

7.2 Modern Organosilicon Cross-Coupling 479

7.3.1 The Pentacoordinate Silicon 513

7.3.2 Substituent Steric Effects 515

7.3.3 Convergence of Mechanistic Pathways 517

7.3.4 Kinetic Analysis and Mechanistic Implications 519

7.4 Applications to Total Synthesis 524

7.6 Experimental Procedures 525

7.6.1 TBAF-Promoted Palladium-Catalyzed Cross-Coupling of

Alkenylsilanes with Aryl or Alkenyl Halides ((1E)-1-Heptenylbenzene (E)-14) 525

7.6.2 Palladium-Catalyzed Cross-Coupling of

(4-Methoxyphenyl)-dimethylsilanol with 4-Substituted Aryl Iodides

4-Carbethoxy-4-methoxybiphenyl (65) 526

7.6.3 One-Pot Sequential Hydrosilylation/Cross-Coupling Reaction

(E)-5-(4-Methoxyphenyl)-4-penten-1-ol (96) 526

7.6.4 Palladium-Catalyzed Cross-Coupling of Phenyltrimethoxysilane with

Aryl Iodides 4-Acetylbiphenyl 527

7.6.5 One-Pot Sequential Mizoroki–Heck/Cross-Coupling Reaction

(E)-4-[2-(4-Acetylphenyl)-1-butylethenyl]benzoic Acid Ethyl Ester

(171) 527

References 528

Trang 19

8.2.4 Effects of Bases, Ligands, and Additives 544

8.2.5 The Leaving Groups 551

8.2.6 Structural Requirements in Intramolecular Cyclizations 556

8.3 Cascade Reactions and Multiple Couplings 557

8.3.1 Heck Cascades Involving C(sp2) Centers 558

8.3.2 Heck Reaction Cascades Involving C(sp2) and C(sp) Centers 561

8.3.3 Cascades Consisting of Heck and Subsequent Cycloaddition or

Electrocyclization Reactions 562

8.3.3.1 Heck–Diels–Alder Cascades 562

8.3.3.2 Heck-6π-Electrocyclization Cascades 564

8.3.4 Heck Reactions Combined with Other Cross-Coupling Processes 566

8.3.5 Palladium-Catalyzed Reactions Involving Nucleophilic

Substrates 570

8.3.6 Heck–Aldol and Heck–Michael Cascades 577

8.3.7 Heck-Type Processes Involving C–H Activation 579

8.3.8 Hydroarylations and Hydroalkenylations – Reductive Heck

Reactions 587

8.3.9 Heck Reactions with Subsequent Incorporation of Carbon

Monoxide 590

8.3.10 The Heck Coupling in Combination with Other Reactions 591

8.3.11 Multiple Heck Couplings 592

8.4 Related Palladium-Catalyzed Reactions 598

8.5 Enantioselective Heck-Type Reactions 601

8.6 Syntheses of Heterocycles, Natural Products, and Other Biologically

Active Compounds Applying Heck Reactions 607

8.7 Carbopalladation Reactions in Solid-Phase Syntheses 620

8.8 The Heck Reaction in Fine Chemicals Syntheses 627

8.10.4 Diethyl 4-Chloro-4-methoxycarbonylspiro[cyclopropane-1,3

-bicyclo-[4.3.0]non-1(6)-ene]-8,8-dicarboxylate (76) 632

8.10.5 (R)-2-Cyclohexenyl-2,5-dihydrofuran (R)-406 632

Trang 20

9.2 Alkynylcopper Reagents 666

9.2.1 The Stephens–Castro Reaction 666

9.2.2 The Sonogashira Reaction 668

9.2.2.1 Mechanism 668

9.2.2.2 The Sonogashira Catalysts 671

9.2.2.3 Amine Bases 684

9.2.2.4 Solvents and Additives 686

9.2.2.5 Protecting Groups and In situ Protodesilylation/Alkynylation 687

9.2.2.6 Recent Extensions to the Sonogashira Cross-Coupling Protocol 689

9.2.2.7 Applications of the Sonogashira Reaction 699

9.2.3 The Cadiot–Chodkiewicz Coupling 702

9.3 Alkynyltin Reagents 706

9.3.1 The Stille Coupling 706

9.3.2 Organotriﬂates in the Stille Coupling 708

9.3.3 Recent Advancements of the Stille Reaction 713

9.3.4 Applications of the Stille Reaction 716

9.4 Alkynylzinc Reagents 717

9.4.1 The Negishi Protocol 717

9.4.2 Applications of the Negishi Cross-Coupling Reaction 721

9.5 Alkynylboron Reagents 724

9.5.1 The Suzuki–Miyaura Coupling 724

9.5.2 Alkynylboron Coupling Partners 725

9.5.3 Application of the Suzuki–Miyaura Reaction 730

9.6 Alkynylsilicon Reagents 731

9.6.1 Alkynylsilane Cross-Couplings – The Sila–Sonogashira–Hagihara

Reaction 731

9.6.2 One-Pot Twofold Cross-Couplings 735

9.7 Alkynylmagnesium Reagents – The Kumada–Corriu Reaction 736

Trang 21

9.10 Experimental Procedures 746

9.10.1 The Castro–Stephens Reductive Ene–Yne Macrocyclization to 7 746

9.10.2 One-Pot Sonogashira Coupling through In situ TMS Deprotection

to 43 746

9.10.3 Sonogashira Coupling to the Triphenylene Derivative 66 747

9.10.4 The Cadiot–Chodkiewicz Active Template Synthesis of the [2]Rotaxane

74 747

9.10.5 Pd-Free Stille Coupling to the Enyne 85 747

9.10.6 The Suzuki Coupling to Alkynylated

10.6.1 Tertiary Alcohols 40 by Alkylation/Arylation Reactions of

Alkenylcarbamates and Quenching with t-BuONO 867

10.6.2 General Procedure for the Preparation of Alkylidenecyclopropane

Trang 22

11.2.1.4 Addition of Active Methylene Compounds 879

11.3.1.4 1,4-Oxyamination and 1,4-Chloroamination 913

11.3.1.5 Intramolecular 1,4-Additions with C–C Bond Formation 915

References 919

12.2 Palladium-Catalyzed Allylic Alkylations 926

12.2.1 Mechanistic Aspects 926

12.2.1.1 Formation and Reactions ofπ-Allylpalladium Complexes 926

12.2.1.2 Isomerizations ofπ-Allylpalladium Complexes 927

12.2.1.3 Regioselectivity 929

12.2.1.4 Stereochemical Aspects 932

12.2.2 Allylic Substrates for Allylic Alkylations 942

12.2.2.1 Allylic Alkylations under Basic Conditions 942

12.2.2.2 Allylic Alkylations under Neutral Conditions 945

12.2.3 Nucleophiles for Allylic Alkylations 946

12.2.3.1 Reactions with Stabilized, ‘‘Soft’’ Nucleophiles 946

12.2.3.2 Reactions with Enolates and Their Derivatives 948

12.2.3.3 Reactions with Hard Nucleophiles 953

12.2.4 Carbonylations 954

12.2.5 Umpolung ofπ-Allylpalladium Complexes 955

12.3 Allylic Alkylations with Other Transition Metals 959

12.3.1 Iridium 959

12.3.2 Iron 964

12.3.3 Molybdenum 966

12.3.4 Nickel 969

Trang 23

12.4.2 Iridium-Catalyzed Asymmetric Allylic Alkylation 983

12.4.3 Ruthenium-Catalyzed Allylation of 1,3-Diketones with Allyl

Jan Paradies

14 The Directed Ortho Metallation (DoM)–Cross-Coupling Nexus.

Tetsuya Satoh and Masahiro Miura

Index 1495

Trang 25

Preface XV

Reactions 1

Shiqing Xu, Hirofumi Kamada, Eun Hoo Kim, Akimichi Oda,

and Ei-ichi Negishi

4 Carbon–Carbon Bond Forming Reactions Mediated by Organozinc

Trang 26

Reaction 533

Stefan Br¨ase and Armin de Meijere

10 Carbometallation Reactions 763

Ilan Marek and Yury Minko

11 Palladium-Catalyzed 1,4-Additions to Conjugated Dienes 875

Jan-Erling B¨ackvall

13.4.1.2 Primary Aliphatic Amines 1012

13.4.1.3 Cyclic Secondary Aliphatic Amines 1020

13.4.1.4 Acyclic Secondary Aliphatic Amines 1025

13.4.1.5 Arylation of Aniline Derivatives 1030

Trang 27

13.4.2 Arylation of Amide, Urethane, Urea, and Sulfonic Acid Amide

13.8.1 Synthesis of Anilines from Aryl Halides and Ammonia 1056

13.8.2 Coupling of Primary Aliphatic Amines 1056

13.8.3 Coupling of Cyclic Secondary Aliphatic Amines 1057

13.8.4 Coupling of Acyclic Secondary Aliphatic Amines 1057

13.8.5 Coupling of Diarylanilines 1058

13.8.6 Arylation of Amides 1059

13.8.7 Amination with C–H Bond Activation 1059

References 1060

14 The Directed Ortho Metallation (DoM)–Cross-Coupling Nexus.

14.2 Content of this Review 1070

14.3 Synthetic Methodology Derived from the DoM–Cross-Coupling

14.3.1.3 Li→ Sn Transmetallation The Migita–Stille Cross-Coupling 1090

14.3.1.4 Li→ Zn Transmetallation The Negishi Cross-Coupling 1093

14.3.2 Comparison of Named C–C Cross-Coupling Reactions in the DoM

Context 1095

14.3.2.1 Directed Remote Metallation (DreM) Connections 1097

14.3.3 DoM–C–N, C–O, and C–S Cross-Couplings Methodology for

Ar–Z–Ar Systems 1098

14.3.3.1 DreM Connection 1100

14.4 Application in Synthesis 1101

14.4.1 Synthesis of Bioactive Molecules 1101

14.4.1.1 DoM–Cross-Coupling Tactics Involving Ar–Ar Bond

Formation 1101

14.4.1.2 DoM–Cross-Coupling Tactics Involving Ar–Z–Ar Bond

Formation 1106

Trang 28

14.4.2 Synthesis of Natural Products 1106

14.4.2.1 The Suzuki–Miyaura Cross-Coupling 1106

14.4.2.2 The Migita–Stille Cross-Coupling 1110

14.4.2.3 The Negishi Cross-Coupling 1115

14.4.3 Synthesis of Organic Materials 1116

14.5 Conclusions and Prognosis 1119

14.5.1 Synthetic Methodology 1119

14.5.2 Synthetic Applications 1120

14.5.3 Prognosis 1120

14.6 Selected Experimental Procedures 1121

14.6.1 The DoM–Suzuki–Miyaura Cross-Coupling for the Preparation of

14.6.6 DoM–Ullmann Cross-Coupling Synthesis of Ar–X–Ar(X=O, N, S)

under Modiﬁed Ullmann Reaction Conditions 1124

14.6.7 Typical Buchwald–Hartwig Cross-Coupling Procedure Synthesis of

N,N-Diethyl-N-phenylanthranilamide 1124

Acknowledgments 1124

References 1125

15.2 Early Transition Metal Catalysts 1136

15.2.1 Introduction 1136

15.2.2 Catalysts for Alkyne Hydroamination 1139

15.2.3 Catalysts for Allene Hydroamination 1145

15.2.4 Catalysts for Alkene Hydroamination 1146

15.2.4.1 Expanded Substrate Scope 1148

15.2.4.2 Secondary Amine Substrates 1151

15.2.4.3 Mechanistic Insights 1152

15.2.4.4 Room Temperature Reactivity 1153

15.2.5 Catalysts for Asymmetric Alkene Hydroamination 1156

Trang 29

15.3.1.2 Nucleophilic Attack on Allylic Complexes 1162

15.3.1.3 Insertion Route for C–N Bond Formation 1163

15.3.2 Hydroamination of Ethylene 1165

15.3.3 Hydroamination with Ammonia 1169

15.3.4 Catalysts for Alkyne Substrates 1171

15.3.5 Catalysts for Allene Substrates 1183

15.3.6 Catalysts for Alkene Substrates 1189

15.3.6.1 Intermolecular Alkene Hydroamination 1197

15.3.6.2 Intramolecular Alkene Hydroamination 1200

15.5 Summary and Future Directions 1244

15.6 Example Experimental Procedures 1245

15.6.1 Alkene Hydroamination with Ti(NMe2)4 1245

15.6.2 Alkene hydroamination with [Ir(COD)Cl]2 1245

15.6.3 Allene Hydroamination with Zirconium Ureate Complex (5) 1246

15.6.4 Allene Hydroamination with (dppf)PtCl2 1246

15.6.5 Asymmetric Hydroamination with Chiral Zwitterionic Zr Complex

19 1246

15.6.6 Asymmetric Hydroamination with a Chiral Rh Complex Using Ligand

64 1247

15.6.7 Ethylene Hydroamination 1247

15.6.8 Hydroamination with Ammonia 1248

15.6.9 Alkyne Hydroamination with Au-CAAC Complex 1248

References 1248

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16.4.3.1 Experimental Procedure for Catalytic Enantioselective

Carboamination 1284

16.5 Metal-Catalyzed Difunctionalization of Alkenes 1286

16.5.1 Intramolecular Processes 1288

16.5.1.1 Tethered Amination Reactions 1288

16.5.1.2 Copper-Assisted Nucleophilic Palladium Displacement 1288

17.2 C–H/C–X Coupling 1316

17.2.1 Early Contributions 1316

17.2.2 With Directing Group (Chelation-Assisted Arylation) 1318

17.2.2.1 Early Contributions of C–H/C–X Coupling with Directing

17.2.4 C–H/C–X Coupling of Various Heteroarenes and Aryl Halides 1329

17.2.4.1 Indoles and Pyrroles – Electron-Rich Heteroarenes 1329

17.2.4.2 Thiophenes and Furans – Electron-Rich Heteroarenes 1334

17.2.4.3 1,3-Azoles and Derivatives – Electron-Neutral Heteroarenes 1340

17.2.4.4 Azines and Related Electron-Deﬁcient Heteroarenes 1346

17.2.4.5 Miscellaneous Azoles and Azines 1348

17.3 ‘‘Special’’ Coupling Partners: Phenol Derivatives and Arylcarbonyl

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17.5.2.3 C–H/C–H Cross-Coupling of Heteroarenes and Arenes 1368

17.5.2.4 Oxidative C–H/C–H Cross-Coupling of Heteroarenes 1371

18.2 Oxidative C–H Bond Alkenylation with Alkenes 1390

18.2.1 The Fujiwara–Moritani-Type Reaction 1390

18.2.2 Chelate-Directed Alkenylation (Ortho Alkenylation) 1392

18.2.3 Regioselective Alkenylation of Heteroarenes 1403

18.3 Direct C–H Bond Alkenylation with Alkenyl Halides and Alkenylmetal

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19.2.3 C–H Alkylation Catalyzed by First-Row Transition Metals 1447

19.3 C–H Alkylation with Alkylmetal Reagents 1451

19.5.1 Palladium-Catalyzed ortho-Triﬂuoromethylation of Arenes 1484

19.5.2 Palladium-Catalyzed Direct C-2 Alkylation of Free N–H Indoles 1485

19.5.3 Palladium-Catalyzed Direct Benzylation of Heteroarenes 1485

19.5.4 Iron-Catalyzed Alkylation of (Hetero)arenes 1486

19.5.5 C(sp3)–H Alkylation with Boronic Acids Directed by O-Methyl

Hydroxamic Acids 1486

19.5.6 In Situ Generation of a Tunable Catalyst 1486

19.5.7 Intermolecular Alkylation of Heteroarenes 1487

19.5.8 Nickel-Catalyzed C-4 Alkylation of Pyridines 1487

References 1488

Index 1495

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As a quick survey of the chemical literature in the last 30 years discloses, research inthe area of Organometallic Chemistry is more productive than ever, and new metal-catalyzed carbon–carbon as well as carbon–heteroatom bond-forming reactionsconstitute a major fraction of it This was underscored again by the recent 17thSymposium on ‘‘Organometallic Chemistry Towards Organic Synthesis (OMCOS17)’’ held in Fort Collins, Colorado, USA, at which 6 out of 8 Plenary, 6 out of 12Invited and 7 out of 12 Short lectures as well as 101 out of 347 Posters dealt with

‘‘Metal-Catalyzed Cross-Coupling Reactions’’ in the broader sense This series ofconferences, which was initiated by Louis S Hegedus and John K Stille in 1981with the ﬁrst of its kind in Fort Collins, has been ever since growing in attendancerecord and visibility The fact that the Nobel Prize in Chemistry was awarded toRichard Heck, Ei-ichi Negishi, and Akira Suzuki in 2010 for their seminal work

on such cross-coupling reactions, emphasized the necessity for producing an to-date monograph on this topic, after the ﬁrst one came out in 1998 followed by

up-a second completely revised up-and enlup-arged edition in 2004 As this ﬁeld hup-as grown

so much and keeps growing further, the editors in consent with the Wiley-VCHpublisher decided to bring out a new book under the title ‘‘Metal-Catalyzed Cross-Coupling Reactions and More’’ to express the fact that the recent developmentbrings forward more and more sequential reactions incorporating cross-couplings

as one of the steps and that C–H bond activation has started to play a majorrole The latter type of reaction certainly is not a cross-coupling in the originaldeﬁnition, but the outcome is the same Accordingly, ﬁve new chapters have beenincorporated in the new book, while one of the previous chapters has been droppedfor lack of progress in the area For reasons of comprehensiveness, two chaptershave simply been reprinted, as other comprehensive and up–to–date reviews onthe corresponding topics have recently been published in other contexts All of theremaining 12 chapters have been updated or completely rewritten with a focus onnew developments during the last 10 years All in all, this three-volume monograph

is meant to provide a useful and rather complete overlook of the particular area ofOrganometallic Chemistry

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It is due to all of the engaged authors that this book came into being, and theeditors wish to express their sincere thanks for all the efforts by the authors as well

as the team at Wiley-VCH

Martin Oestreich

Trang 35

Fritz-Haber-Weg 6

76131 KarlsruheGermany

Anton Bayer

Saarland UniversityInstitute for Organic ChemistryCampus C4.2

66123 Saarbr¨uckenGermany

Fabrice Chemla

Universit´e Pierre et MarieCurie Paris 6

UMR CNRS 7201 – InstitutParisien de Chimie Mol´eculaire(FR 2769), Case 183

4 Place Jussieu

75252 Paris Cedex 5France

Scott E Denmark

Department of ChemistryUniversity of Illinois

600 South Mathews AvenueUrbana, IL 61801

USA

Trang 36

Bio-Molecules (WPI-ITbM) and

Graduate School of Science

4 Place Jussieu

Rodolphe Jazzar

Université Claude BernardLyon 1, CNRS UMR 5246Institut de Chimie etBiochimie Moléculaires etSupramoléculaires, CPE Lyon

43 Boulevard du 11Novembre 1918

69622 VilleurbanneFrance

Ludivine Jean-G´erard

Université Claude BernardLyon 1, CNRS UMR 5246Institut de Chimie etBiochimie Moléculaires etSupramoléculaires, CPE Lyon

43 Boulevard du 11Novembre 1918

69622 VilleurbanneFrance

Hirofumi Kamada

Purdue UniversityBrown Laboratory of Chemistry

560 Oval DriveWest Lafayette, IN 47907-2084USA

Uli Kazmaier

Saarland UniversityInstitute for Organic ChemistryCampus C4.2

66123 Saarbr¨uckenGermany

Trang 37

Eun Hoo Kim

University of Erlangen-N¨urnberg

Department of Chemistry and

Schulich Faculty of Chemistry

and The Lise Meitner-Minerva

Center for Computational

Svante Arrhenius v¨ag 16 C

10691 StockholmSweden

Armin de Meijere

Georg-August-Universit¨atG¨ottingen

Institut f¨ur Organische undBiomolekulare ChemieTammannstrasse 2

37077 G¨ottingenGermany

Laurent Micouin

UMR CNRS 8601 - Laboratoire deChimie et Biochimie

Pharmacologiques etToxicologiques

45, Rue des Saints-P `eres

75006 ParisFrance

Yury Minko

Technion – Israel Institute

of TechnologySchulich Faculty of Chemistryand The Lise Meitner-MinervaCenter for ComputationalQuantum ChemistryHaifa 32000Israel

Terence N Mitchell

Technische Universit¨atDortmund, Organische ChemieOtto-Hahn-Str 6

44227 DortmundGermany

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Kilian Mu˜ niz

Institute of Chemical Research of

Catalan Institution for Research

and Advanced Studies (ICREA)

4 Place Jussieu

and

UMR 8601 CNRS-Paris DescartesLaboratoire de Chimie et deBiochimie pharmacologiques

et toxicologiques 45rue des Saints P `eres

75006 ParisFrance

Tetsuya Satoh

Osaka UniversityDepartment of Applied ChemistryFaculty of Engineering

2-1 Yamadaoka SuitaOsaka 565-0871Japan

Laurel L Schafer

University of British ColumbiaDepartment of Chemistry

2036 Main MallVancouver, BC V6T 1Z1Canada

Tobias A Schaub

University of Erlangen-N¨urnbergDepartment of Chemistry andPharmacy

Chair of Organic Chemistry IHenkestrasse 42

91054 ErlangenGermany

Trang 39

Jacky C.-H Yim

Neal Yonson

Tiêu đề	Metal-Catalyzed Cross-Coupling Reactions and More
Tác giả	Armin De Meijere, Stefan Bräse, Martin Oestreich
Thể loại	edited book
Năm xuất bản	2014

Định dạng
Số trang	1.551
Dung lượng	12,73 MB