Contents to Volume 1

Preface XV List of Contributors XVII

Mechanistic Aspects of Metal-Catalyzed C,C- and C,X-Bond Forming Reactions 1 Antonio M. Echavarren and Anna Homs

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

Pd-Catalyzed Cross-Coupling with Organometals Containing Zn, Al, Zr, and so on - The Negishi Coupling and Its Recent Advances 133 Shiqing Xu, Hirojumi Kamada, Eun Hoo Kim, Akimichi Oda, and Ei-ichi Negishi

Carbon-Carbon Bond Forming Reactions Mediated by Organozinc Reagents 279 Fabrice Chemla, Franck Ferreira, Olivier Jackowski, Laurent Micouin, and Alejandro Perez-Luna

Carbon-Carbon-Bond-Forming Reactions Mediated by Organomagnesium Reagents 365 Fabrice Chemla, Franck Ferreira, Alejandro Perez-Luna, Laurent Micouin, and Olivier Jackowski

Organotin Reagents in Cross-Coupling Reactions 423 Belen Martin-Matute, Kdlman J. Szabd, and Terence N. Mitchell

http://d-nb.info/1046968165 VII Contents

Contents to Volume 2

List of Contributors XIII

7 Organosilicon Compounds in Cross-Coupling Reactions 475 Scott E. Denmark and Ramzi F. Sweis 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 7.2.1 Organosiletanes 479 7.2.2 Organosilanols 482 7.2.2.1 Tetrabutylammonium Fluoride (TBAF)-Promoted Coupling 483 7.2.2.2 Non-Fluoride-Promoted Coupling 488 7.2.3 Organosiloxanes 494 7.2.4 Organosilyl Ethers 497 7.2.5 Organopyridyl- and Organothiophenylsilanes 506 7.2.6 Organosilyl Hydrides 511 7.3 Mechanistic Studies in Silicon-Based Cross-Coupling Reactions 513 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 7.5 Summary and Outlook 525 7.6 Experimental Procedures 525 7.6.1 TBAF-Promoted Palladium-Catalyzed Cross-Coupling of Alkenylsilanes with Aryl or Alkenyl Halides. ((1£)-1 -Heptenylbenzene (£)-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. (£)-5-(4-Methoxyphenyl)-4-penten-l-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)-l-butylethenyl]benzoic Acid Ethyl Ester (171) 527 List of Abbreviations 527 References 528 Contents |VII

8 Cross-Coupling of Organyl Halides with Alkenes - The Heck Reaction 533 Stefan Bra.se and Armin de Meijere 8.1 Introduction 533 8.2 Principles 534 8.2.1 The Mechanism 534 8.2.2 The Catalysts 536 8.2.3 The Alkenes 541 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 Cydoaddition or Electrocydization Reactions 562 8.3.3.1 Heck-Diels-Alder Cascades 562 8.3.3.2 Heck-6ji-Electrocydization Cascades 564 8.3.4 Heck Reactions Combined with Other Cross-Coupling Processes 566 8.3.5 Palladium-Catalyzed Reactions Involving Nudeophilic 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 Heterocydes, 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 8.9 Conclusions 628 8.10 Experimental Procedures 629 8.10.1 Dipotassium (E)-4,4'-Diphenylstilbene-4",4"'-disulfonate (Stilbene I) (I2-SO3K) 629 8.10.2 trans-4-Acetylstilbene (480) 630 8.10.3 Methyl 3-(£)-{2-[2-(£)-Methoxycarbonylethenyl]cyclopent-l-enyl} acrylate (482b) 631 8.10.4 Diethyl 4' -Chloro-4' -methoxycarbonylspiro[cy dopropane-1,3' -bicydo- [4.3.0]non-l'(6')-ene]-8',8'-dicarboxylate (76) 632 8.10.5 (R)-2-Cydohexenyl-2,5-dihydrofuran (i?)-406 632 VIIII Contents

8.10.6 6-Methoxy-l-(S)-ethenyl-l,2,3,4-tetrahydronaphthalene (26) 633 8.10.7 10,ll-Benzo-13-oxatricydo[7.4.1.01'6]tetradeca-3,7-diene-6-carbonitrile (362) 633 8.10.8 Hexakismethanofullerene Derivative 294 634 Acknowledgments 635 List of Abbreviations 635 References 637

9 Cross-Coupling Reactions to sp Carbon Atoms 665 Tobias A. Schaub and Milan Kivala 9.1 Introduction 665 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 9.8 Other Alkynylmetals 739 9.8.1 Alkynylaluminum Reagents 739 9.8.2 Alkynylindium Reagents 741 9.8.3 Alkynylgermanium, Alkynylsilver, and Alkynylmanganese Reagents 743 9.9 Concluding Remarks 745 Contents IIX

9.10 Experimental Procedures 746 9.10.1 The Castro-Stephens Reductive Ene-Yne Macrocydization 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 Naphthalene-Tricarbonylchromium Complexes 117 748 Acknowledgments 748 List of Abbreviations 748 References 750

10 Carbometallation Reactions 763 Ilan Marek and Yury Minko 10.1 Introduction 763 10.2 Carbometallation of Alkenes 764 10.2.1 Intermolecular Reactions 764 10.2.2 Intramolecular Reactions 798 10.3 Carbometallation of Alkynes 816 10.3.1 Intermolecular Reactions 816 10.3.2 Intramolecular Reactions 858 10.4 Carbometallation Reactions of Allenes 864 10.5 Conclusions 866 10.6 Experimental Procedures 867 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 Derivatives 83 867 10.6.3 frans,cis-2-Methyl-l-phenyl-l,2,3,5,6,10b-hexahydropyrrolo[2,l-a] isoquinoline 184 868 10.6.4 General Procedure for the One-Pot Formation of the Aldol Surrogate 380 868 10.6.5 Synthesis of Tetrasubstituted 1,3-Dienes 442 868 References 869

11 Palladium-Catalyzed 1,4-Additions to Conjugated Dienes 875 Jan-Erling Backvall 11.1 Introduction 875 11.2 Palladium(0)-Catalyzed Reactions 876 11.2.1 Addition of H-Nu 876 11.2.1.1 1,4-Hydrosilylation 877 11.2.1.2 1,4-Hydrostannation 878 11.2.1.3 1,4-Hydroamination 879 X Contents

11.2.1.4 Addition of Active Methylene Compounds 879 11.2.1.5 1,4-Hydrosulfonation 880 11.2.1.6 1,4-Hydrosulfenation and 1,4-Hydrothiocarbonylation 881 11.2.1.7 1,4-Hydroboration 881 11.2.1.8 1,4-Hydrocyanation 882 11.2.2 1,4-Coupling with a Carbanion Equivalent and Another Nucleophile 882 11.2.2.1 1,4-Carboamination 883 11.2.2.2 1,4-Addition of a Carbon Nucleophile (Aryl or Vinyl) and a Stabilized Carbanion 885 11.2.2.3 1,4-Addition of Carbon and Oxygen 886 11.2.2.4 1,4-Carbosilylation 888 11.3 Palladium(II)-Catalyzed Reactions 890 11.3.1 1,4-Addition of Two Nucleophiles 890 11.3.1.1 1,4-Diacyloxylation 891 11.3.1.2 1,4-Haloacyloxylation 901 11.3.1.3 1,4-Addition of an Alkoxide and Another Oxygen Function or a Halide 909 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 Cross-Coupling Reactions via n-Allylmetal Intermediates 925 Anton Bayer and Uli Kazmaier 12.1 Introduction 925 12.2 Palladium-Catalyzed Allylic Alkylations 926 12.2.1 Mechanistic Aspects 926 12.2.1.1 Formation and Reactions of 7i-Allylpalladium Complexes 926 12.2.1.2 Isomerizations of n-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 of 7t-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 Contents XI

12.3.5 Platinum 971 12.3.6 Rhodium 972 12.3.7 Ruthenium 977 12.3.8 Tungsten 981 12.4 Experimental Procedures 983 12.4.1 Palladium-Catalyzed Asymmetric Tsuji Allylation of Allyl Enol Carbonates 983 12.4.2 Iridium-Catalyzed Asymmetric Allylic Alkylation 983 12.4.3 Ruthenium-Catalyzed Allylation of 1,3-Diketones with Allyl Alcohol 983 12.4.4 Rhodium-Catalyzed Allylic Alkylation of Chelated Enolates 983 List of Abbreviations 984 References 985

Contents to Volume 3

List of Contributors XIII

13 Palladium-Catalyzed Aromatic Carbon-Nitrogen Bond Formation 995 Jan Parodies

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 Mufiiz and Claudio Martinez

17 Biaryl Synthesis through Metal-Catalyzed C-H Arylation 1315 Junichiro Yamaguchi and Kenichiro Itami

18 C-H Bond Alkenylation 1389 Tetsuya Satoh and Masahiro Miura

19 C-H Bond Alkylation (Including Hydroarylation of Alkenes) 1427 Ludivine Jean-Gerard, Rodolphe Jazzar, and Olivier Baudoin

Index 1495