Comprehensive Organometallic Chemistry IV. Volume 12: Applications II. d- and f-Block Metal Complexes in Organic Synthesis - Part 1 12

Comprehensive Organometallic Chemistry, Fifteen Volume Set is the market-leading resource covering all areas of this critical sub-discipline of chemistry. Divided into 15 clear sections, it provides expert coverage of the synthesis, structures, bonding and reactivity of all organometallic compounds, including the mechanisms of the reactions. Applications of organometallic chemistry, such as the role of these compounds as reagents and catalysts for organometallic transformations, and their participation in bioorganometallic chemistry, is then covered. This is a vibrant area, as illustrated by the fact that the 2001, 2005 and 2010 Nobel prizes in Chemistry are all concerned with organometallic chemistry. This new edition will therefore again provide an invaluable and efficient learning resource for all researchers and educators looking for up-to-date analysis of a particular aspect of organometallic chemistry. 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Volume 12: Applications II. d- and f-Block Metal Complexes in Organic Synthesis - Part 1 Copyright Contents of Volume 12 Editor Biographies Contributors to Volume 12 Preface 12.01 Volume 12 and 13: Applications II. d- and f- Block Metal Complexes in Organic Synthesis 12.01.1 Introduction 12.02 C–C Bond Formation Through Heck-Like Reactions Nomenclature 12.02.1. Brief history 12.02.2. Heck reaction of aryl and alkenyl (pseudo)halides 12.02.2.1. Heck reaction of cyclic alkenes 12.02.2.2. Heck reaction of acyclic alkenes 12.02.2.3. Nickel-catalyzed Heck reaction 12.02.2.4. Synthetic applications 12.02.3. Heck-Matsuda reaction 12.02.3.1. Introduction 12.02.3.2. Arylation of cyclic olefins 12.02.3.3. Arylation of acyclic olefins 12.02.4. Heck-type reaction of unactivated alkyl electrophiles 12.02.4.1. Introduction 12.02.4.2. Pd-catalyzed thermal Heck-type alkylation 12.02.4.3. Pd-catalyzed photoinduced Heck-type alkylation 12.02.4.4. Cobalt- and nickel-catalyzed Heck-type alkylation 12.02.5. Heck-type alkylation of activated alkyl halides 12.02.6. Heck reaction of benzylic electrophiles 12.02.7. Heck reaction of allylic and propargylic electrophiles 12.02.7.1. Heck reaction of allylic electrophiles 12.02.7.2. Heck reaction of propargylic electrophiles 12.02.8. Narasaka-Heck reaction 12.02.9. Heck reaction of silyl electrophiles 12.02.10. Heck reaction of boryl electrophiles 12.02.11. Conclusion Acknowledgment References 12.03 Metal-Mediated Reductive C–C Coupling of π Bonds 12.03.1. Introduction 12.03.2. Lanthanides and group 3 metals 12.03.2.1. Stoichiometric reductive coupling of alkenes with aldehydes and ketones 12.03.2.2. Stoichiometric reductive coupling of aldehydes and ketones (pinacol type) 12.03.2.3. Catalytic reductive coupling of alkenes with ketones 12.03.3. Early-mid transition metals 12.03.3.1. Early transition metal-mediated examples 12.03.3.1.1. Stoichiometric early transition metal coupling of alkenes and alkynes 12.03.3.1.2. Stoichiometric couplings of π bonds with aldehydes, imines, ketones, and nitriles 12.03.3.2. Catalytic early transition metal coupling 12.03.3.3. Fe-catalyzed reductive cyclization 12.03.3.4. Ru-catalyzed reductive coupling 12.03.4. Late transition metals 12.03.4.1. Reductive coupling of alkynes and alkenes π bonds 12.03.4.1.1. Hydrosilylation/cyclization 12.03.4.1.2. Dihydrogenative reductive coupling 12.03.4.2. Reductive coupling of alkenes and alkynes with aldehydes and aldimines 12.03.4.2.1. Enantioselective synthesis on unactivated alkenes 12.03.4.2.2. Enantioselective synthesis using alkynes 12.03.4.2.3. Mild reductants 12.03.4.2.4. Tandem reactions 12.03.4.2.5. Miscellaneous noteworthy reactions 12.03.5. Photocatalytic reductive coupling with photoredox reagents 12.03.6. Conclusion References 12.04 C–C Bond Formation Through Cross-Electrophile Coupling Reactions 12.04.1. Introduction 12.04.2. Proposed mechanisms of cross-electrophile coupling (XEC) reactions 12.04.3. XEC reactions employing stoichiometric reductants 12.04.3.1. Reactions of C(sp2) electrophiles (Type A) 12.04.3.1.1. Dimerization reactions of C(sp2) electrophiles 12.04.3.1.2. Cross-selective XEC reactions of C(sp2) electrophiles 12.04.3.2. XEC reactions of C(sp2) and C(sp3) electrophiles (Type B) 12.04.3.2.1. XEC reactions of aryl and vinyl electrophiles with C(sp3) electrophiles 12.04.3.2.2. XEC reactions of acyl electrophiles with C(sp3) electrophiles 12.04.3.2.3. Cyclization reactions of C(sp2) and C(sp3) electrophiles 12.04.3.3. XEC reactions of C(sp3) electrophiles (Type C) 12.04.3.3.1. Dimerization reactions of C(sp3) electrophiles 12.04.3.3.2. Cross-selective XEC reactions of C(sp3) electrophiles 12.04.3.3.3. XEC reactions of allylic trifluoromethyl electrophiles and C(sp3) electrophiles 12.04.3.3.4. Cyclization reactions of C(sp3) electrophiles 12.04.3.3.5. XEC reactions of C(sp) electrophiles (Type D) 12.04.4. XEC reactions employing electrochemical reductions 12.04.4.1. XEC reactions of C(sp2) electrophiles (Type A) 12.04.4.2. XEC reactions of C(sp2) and C(sp3) electrophiles (Type B) 12.04.4.3. XEC reactions of C(sp3) electrophiles (Type C) 12.04.5. XEC reactions in natural product syntheses 12.04.6. Closing remarks Acknowledgment References 12.05 C–C Bond Formation Through C-H Activation 12.05.1. Introduction 12.05.2. Pd-catalyzed CH bond functionalization 12.05.2.1. CH bond arylation 12.05.2.1.1. C(sp2)H bond arylation with aryl halides and aryl organometallic reagents 12.05.2.1.2. C(sp2)H bond arylation with simple aromatic ring 12.05.2.1.3. meta-C(sp2)-H arylation 12.05.2.1.4. C(sp3)-H arylation 12.05.2.1.5. C-H arylation using transient directing group 12.05.2.1.6. Pd(0)-initiated C-H arylation 12.05.2.2. CH bond alkenylation 12.05.2.3. CH bond alkylation 12.05.2.4. CH bond alkynylation 12.05.2.5. Enantioselective C-H activation 12.05.2.6. Applications in organic synthesis 12.05.3. Rh-catalyzed CH bond functionalization 12.05.3.1. CH bond arylation 12.05.3.2. CH bond alkenylation 12.05.3.3. CH bond alkylation 12.05.3.4. CH bond alkynylation 12.05.3.5. CH bond annulation 12.05.3.6. Enantioselective C-H activation 12.05.3.7. Applications in organic synthesis 12.05.4. Concluding remarks References 12.06 Direct C–E (E = Boron, Halogen, Oxygen) Bond Formation Through C–H Activation 12.06.1. Introduction 12.06.2. Metal-catalyzed CB bond formation 12.06.2.1. Ir-catalyzed CH borylation 12.06.2.1.1. Ir-catalyzed non-directed CH borylation 12.06.2.1.2. Ir-catalyzed directed CH borylation 12.06.2.2. Rh-catalyzed CH borylation 12.06.2.3. Pd-catalyzed CH borylation 12.06.2.4. Other metal catalyzed CH borylation 12.06.3. Metal-catalyzed C-X (X=cl, Br, I) bond formation 12.06.3.1. Pd-catalyzed CH halogenation 12.06.3.2. Rh-catalyzed CH halogenation 12.06.3.3. Cu-catalyzed CH halogenation 12.06.3.4. Other metal catalyzed CH halogenation 12.06.4. Metal-catalyzed CO bond formation 12.06.4.1. Pd-catalyzed CH oxygenation 12.06.4.1.1. Pd-catalyzed CH acetoxylation 12.06.4.1.2. Pd-catalyzed CH hydroxylation 12.06.4.1.3. Pd-catalyzed CH lactonization 12.06.4.2. Other metals catalyzed CO bond formation 12.06.5. Conclusion Acknowledgment References 12.07 Synthetic Applications of Carbene and Nitrene C–H Insertion 12.07.1. Introduction 12.07.2. Intermolecular rhodium(II) catalyzed carbene CH insertion 12.07.2.1. Donor/acceptor carbenes 12.07.2.2. Early examples of Rh2(DOSP)4-catalyzed CH functionalization 12.07.2.3. Combined CH functionalization/Cope rearrangement 12.07.2.4. Catalyst-controlled CH functionalization 12.07.2.4.1. Overview of chiral dirhodium catalysts 12.07.2.4.2. Catalyst-controlled selective reactions at unactivated CH bonds 12.07.3. Intramolecular rhodium(II)-catalyzed carbene CH insertion 12.07.3.1. Asymmetric intramolecular carbene CH insertion reactions 12.07.4. Other metal catalysts for asymmetric carbene CH insertion reactions 12.07.4.1. Chiral copper catalysts for asymmetric carbene CH functionalization 12.07.4.2. Chiral rhodium catalysts for asymmetric carbene CH functionalization 12.07.4.3. Chiral ruthenium catalysts for asymmetric carbene CH functionalization 12.07.4.4. Chiral iridium catalysts for asymmetric carbene CH functionalization 12.07.4.5. Chiral cobalt catalyst for asymmetric carbene CH functionalization 12.07.5. Biocatalysts and metalloenzymes for asymmetric carbene CH insertion reactions 12.07.6. Nitrene CH insertion 12.07.6.1. Rhodium(II)-catalyzed nitrene CH insertion 12.07.6.1.1. Intramolecular nitrene CH insertion 12.07.6.1.2. Intermolecular nitrene CH insertion 12.07.6.1.3. Enantioselective CH amination 12.07.6.1.4. Applications in total synthesis 12.07.6.2. Manganese-catalyzed nitrene CH insertion 12.07.6.3. Ruthenium-catalyzed nitrene CH insertion 12.07.6.4. Copper-catalyzed nitrene CH insertion 12.07.6.5. Silver-catalyzed nitrene CH insertion 12.07.6.6. Gold-catalyzed CH amination 12.07.6.7. Cobalt-catalyzed nitrene CH insertion 12.07.6.8. Iron-catalyzed nitrene CH insertion Acknowledgment References 12.08 Metal-Catalyzed Amination: C–N Bond Formation 12.08.1. Amination of aliphatic Csp3H bonds 12.08.1.1. Csp3H bond amination by catalyzed nitrene transfer reaction 12.08.1.1.1. Racemic nitrene transfer reactions 12.08.1.1.2. Enantioselective variants 12.08.1.2. Csp3H bond amination by SET photoredox catalysis and electrochemical oxidation 12.08.1.2.1. Intramolecular amination 12.08.1.2.2. Intermolecular amination 12.08.1.3. Csp3H bond amination by CH activation 12.08.1.3.1. Intramolecular amination 12.08.1.3.2. Intermolecular CH amination 12.08.2. Allylic amination for the construction of Csp3N bonds 12.08.2.1. Introduction 12.08.2.2. Asymmetric amination through allylic substitution 12.08.2.3. Amination of alkynes and allenes 12.08.2.3.1. Pd-catalyzed hydroamination of alkynes and allenes 12.08.2.3.2. Rh-catalyzed hydroamination of alkynes and allenes 12.08.2.3.3. Au-catalyzed hydroamination of alkynes and allenes 12.08.3. Vinylic Csp2N bond formation 12.08.3.1. Transition metal catalyzed hydroamination of alkynes 12.08.3.2. Vinylic amination by cross-coupling 12.08.4. Aromatic Csp2N bond formation 12.08.4.1. The Ullmann-Goldberg reaction 12.08.4.2. The Buchwald Hartwig amination 12.08.4.2.1. Bulky biarylphosphine ligands 12.08.4.2.2. Bisphosphine ligands 12.08.4.2.3. Ni-catalyzed Buchwald-Hartwig amination 12.08.4.3. The Chan-Lam amination 12.08.5. Conclusion References 12.09 Synthetic Applications of C–C Bond Activation Reactions 12.09.1. Introduction 12.09.2. C-C activation with (benzo)cyclobutenones in total synthesis 12.09.3. C-C activation with cyclobutanones in total synthesis 12.09.4. C-C activation with cyclobutanols and cyclopropanols in total synthesis 12.09.5. Conclusion Acknowledgment References 12.10 Synthetic Applications of C–O and C–E Bond Activation Reactions 12.10.1. Introduction 12.10.2. C-O bond activation 12.10.2.1. Overview 12.10.2.2. C(sp)-O bond activation 12.10.2.3. C(aryl)-O bond activation 12.10.2.3.1. Aryl esters and derivatives 12.10.2.3.2. Aryl ethers 12.10.2.3.3. Arenols 12.10.2.4. C(alkenyl)-O bond activation 12.10.2.5. C(acyl)-O bond activation 12.10.2.6. C(sp3)-O bond activation 12.10.3. C-S bond activation 12.10.3.1. Overview 12.10.3.2. C(sp)-S bond activation 12.10.3.3. C(sp2)-S bond activation 12.10.3.4. C(acyl)-S bond activation 12.10.3.5. C(sp3)-S bond activation 12.10.4. C-N bond activation 12.10.4.1. Overview 12.10.4.2. C(sp)-N bond activation 12.10.4.3. C(aryl)-N bond activation 12.10.4.3.1. The use of a directing group 12.10.4.3.2. No directing group 12.10.4.4. C(acyl)-N bond activation 12.10.4.5. C(sp3)-N bond activation 12.10.5. C-Si bond activation 12.10.5.1. Overview 12.10.5.2. C-Si bond activation of strained silacycles 12.10.5.3. C(sp3)-Si bond activation 12.10.5.4. C(sp2)-Si bond activation 12.10.5.5. C(sp)-Si bond activation 12.10.6. C-P bond activation 12.10.6.1. Overview 12.10.6.2. Phosphoniums 12.10.6.3. Phosphines 12.10.6.3.1. Intermolecular reactions 12.10.6.3.2. Intramolecular cyclizations 12.10.6.4. Phosphoric acid derivatives and phosphine oxides 12.10.7. Conclusion and outlook References 12.11 C–F Bond Activation Reactions 12.11.1. Introduction and overview 12.11.1.1. Introduction 12.11.1.2. Overview of C(sp3)F bond activation4,6,8,12-15,20,22 12.11.1.3. Overview of alkene C(sp2)F bond activation9,14,16,23 12.11.1.4. Overview of arene C(sp2)F bond activation2,3,7,10,11,23 12.11.2. Survey of C(sp3)F bond activation 2005-mid 2021 12.11.2.1. Activation of allylic CF bonds 12.11.2.1.1. SN2-type reaction 12.11.2.1.2. Lewis acid-assisted SN2-type reaction 12.11.2.1.3. SN1 reaction 12.11.2.1.4. Oxidative addition 12.11.2.1.5. Electron transfer 12.11.2.1.6. Addition-β-fluorine elimination 12.11.2.1.6.1. Insertion 12.11.2.1.6.2. Oxidative cyclization 12.11.2.1.6.3. Radical addition 12.11.2.2. Activation of propargylic CF bonds 12.11.2.2.1. Addition-β-fluorine elimination 12.11.2.3. Activation of benzylic CF bonds 12.11.2.3.1. Metalation (oxidative addition and electron transfer) 12.11.2.3.2. Fluoride abstraction 12.11.2.4. Activation of alkyl CF bonds 12.11.2.4.1. SN2 reaction 12.11.2.4.2. Addition-β-fluorine elimination 12.11.2.4.3. Fluoride abstraction 12.11.3. Survey of alkene C(sp2)F bond activation 2005-mid-2021 12.11.3.1. Activation of vinylic CF bonds 12.11.3.1.1. SNV reaction 12.11.3.1.2. Metalation (oxidative addition and electron transfer) 12.11.3.1.3. Addition-β-fluorine elimination 12.11.3.1.3.1. Insertion 12.11.3.1.3.2. Carbo(hetero)metalation 12.11.3.1.3.3. Oxidative cyclization 12.11.3.1.3.4. Radical addition 12.11.3.1.4. Addition-α-fluorine elimination 12.11.3.2. Activation of allenylic CF bonds 12.11.3.2.1. Fluoride abstraction 12.11.3.3. Activation of acyl CF bonds 12.11.3.3.1. Carbonyl-retentive coupling 12.11.3.3.2. Decarbonylative coupling 12.11.4. Survey of arene C(sp2)F bond activation 2005-mid-2021 12.11.4.1. Activation of aromatic CF bonds (1): Directed systems 12.11.4.1.1. Metalation 12.11.4.1.2. CC and CX bond formation 12.11.4.1.2.1. Alkylation and alkoxylation 12.11.4.1.2.2. Arylation, alkenylation, and borylation 12.11.4.1.2.3. CF/CH coupling 12.11.4.1.2.4. Insertion 12.11.4.2. Activation of aromatic CF bonds (2): Nondirected systems with multiple fluorine atoms 12.11.4.2.1. Metalation 12.11.4.2.1.1. SNAr-like metalation (type A) 12.11.4.2.1.2. Ligand-assisted metalation (type B) 12.11.4.2.1.3. Oxidative addition (type C) 12.11.4.2.2. CC and CX bond formation 12.11.4.2.2.1. Alkylation and alkynylation 12.11.4.2.2.2. Arylation 12.11.4.2.2.3. Borylation 12.11.4.2.2.4. Miscellaneous 12.11.4.3. Activation of aromatic CF bonds (3): Nondirected systems with one fluorine atom 12.11.4.3.1. Metalation 12.11.4.3.2. CC and CX bond formation 12.11.4.3.2.1. Activated monofluoroarenes 12.11.4.3.2.2. Nonactivated monofluoroarenes 12.11.4.4. Activation of aromatic CF bonds (4): Miscellaneous 12.11.4.4.1. Carbene analog insertion 12.11.4.4.2. Aryne formation 12.11.4.4.3. SNAr reaction 12.11.4.4.4. Fluoride abstraction 12.11.5. Conclusions and perspectives References 12.12 Polymerization Reactions via Cross Coupling Nomenclature Polymers Metal catalysts Ancillary ligands Solvents Miscellaneous reagents and terms 12.12.1. Introduction 12.12.1.1. Electrophilic and nucleophilic reactive groups 12.12.2. Organomagnesium, organozinc, and organolithium coupling (Kumada-Tamao, Negishi, and Murahashi reactions) 12.12.2.1. General considerations 12.12.2.2. Chain-growth polymerization 12.12.2.2.1. Ligands and catalysts for chain-growth polymerization 12.12.2.2.2. Recent developments in chain-growth polymerization 12.12.2.3. Murahashi coupling 12.12.3. Organotin coupling (Stille-Migita-Kosuke reaction) 12.12.3.1. General considerations 12.12.3.2. AA/BB type coupling of organotin monomers 12.12.3.3. Recent developments in vinylene-based conjugated polymers 12.12.3.4. Polymerization of AB monomers 12.12.4. Organosilicon coupling (Hiyama-Denmark-Ito reaction) 12.12.5. Organoboron coupling (Suzuki-Miyaura reaction) 12.12.5.1. General considerations 12.12.5.2. Boron substituents 12.12.5.3. Polyphenylene derivatives synthesized from AA/BB monomers 12.12.5.4. Masked boronic acids in Suzuki-Miyaura cross-coupling polymerization 12.12.5.5. Chain-growth polymerization 12.12.6. Direct arylation polymerization (CH activation) 12.12.6.1. General considerations 12.12.6.2. Selected examples of DArP 12.12.6.3. Chain-growth polymerization 12.12.7. Oxidative coupling (CH activation) 12.12.7.1. General considerations 12.12.7.2. Glaser-Hay coupling 12.12.7.3. Oxidative polymerization of thiophene derivatives 12.12.8. Dehalogenative coupling (Yamamoto reaction) 12.12.9. Alkene coupling (Mizoroki-Heck reaction) 12.12.9.1. General considerations 12.12.9.2. Polymers synthesized via Mizoroki-Heck polycondensation 12.12.10. Alkyne coupling (Sonogashira-Hagihara reaction) 12.12.10.1. General considerations 12.12.10.2. Typical synthetic approach to PAEs 12.12.10.3. PAE variants synthesized using Sonogashira-Hagihara polymerization 12.12.10.4. Chain-growth polymerization for PAEs 12.12.11. Amine coupling (Buchwald-Hartwig amination reaction) 12.12.11.1. General considerations 12.12.11.2. AA/BB and AB approaches to polyarylamines 12.12.11.3. Dehalogenative polymerization to synthesize polyanilines 12.12.11.4. Polyanilines prepared by chain-growth polymerization 12.12.12. Conclusions Acknowledgment References Cover back