Comprehensive Organometallic Chemistry IV. Volume 11: Applications I. Main Group Complexes in Organic Synthesis

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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. Cover Half Title Comprehensive Organometallic Chemistry IV. Volume 11: Applications I. Main Group Complexes in Organic Synthesis Copyright Contents of Volume 11 Editor Biographies Contributors to Volume 11 Preface 11.01 Overview and Introduction 11.02 Lithium Complexes in Organic Synthesis 11.02.1. Introduction 11.02.2. Preparation of lithium reagents 11.02.3. Reactivity of lithium reagents 11.02.4. Functionalized lithium complexes in synthesis 11.02.4.1. Use of oxygen-bearing lithium compounds in synthesis 11.02.4.2. Use of nitrogen-bearing lithium compounds in synthesis 11.02.4.3. Use of sulfur-bearing lithium compounds in synthesis 11.02.4.4. Use of phosphorous-bearing lithium compounds in synthesis 11.02.4.5. Use of boron-bearing lithium compounds in synthesis 11.02.4.6. Use of halogen-bearing lithium compounds in synthesis 11.02.5. Special lithium complexes 11.02.5.1. Carbamoyllithiums 11.02.5.2. Strained lithium compounds 11.02.5.3. Secondary lithium compounds 11.02.6. Diverse reactions of lithium compounds 11.02.6.1. Rearrangements and migrations 11.02.6.2. Directed lithiations 11.02.6.3. Cross couplings with lithium compounds 11.02.7. Flow technology and flash chemistry with lithium compounds 11.02.8. Conclusions References 11.03 Sodium and Potassium Complexes in Organic Synthesis 11.03.1. Introduction and background 11.03.2. Sodiation/potassiation reagents-Structures and preparation 11.03.2.1. Lochmann-Schlosser bases 11.03.2.2. Alkylsodium and alkylpotassium 11.03.2.3. Sodium and potassium amides 11.03.2.3.1. Sodium 2,2,6,6-tetramethylpiperidide (NaTMP) 11.03.2.3.2. Potassium 2,2,6,6-tetramethylpiperidide (KTMP) 11.03.2.3.3. Sodium diisopropylamide (NaDA) 11.03.2.3.4. Potassium diisopropylamide (KDA) 11.03.3. Metalation 11.03.3.1. Metalation of alkenes 11.03.3.1.1. Metalation of vinylic positions 11.03.3.1.2. Metalation of allylic positions 11.03.3.2. Metalation of (hetero)arenes 11.03.3.3. Metalation of alkyl(hetero)arenes 11.03.3.4. Metalation of carbonyl compounds and their derivatives 11.03.4. Hydroamination of alkenes 11.03.5. Conclusion References 11.04 Magnesium Complexes in Organic Synthesis 11.04.1. Introduction 11.04.2. Stoichiometric reactions 11.04.2.1. Reactions with carbon monoxide 11.04.2.2. Reaction with carbon dioxide 11.04.2.3. Transformations using Mg(I)Mg(I) compounds 11.04.2.4. Reactions with isocyanate 11.04.3. Catalytic reactions 11.04.3.1. Hydrogenation 11.04.3.2. Hydroboration 11.04.3.3. Hydrosilylation 11.04.3.4. Hydrostannylation 11.04.3.5. Dehydrocoupling 11.04.3.6. Hydroamination 11.04.4. Ring-opening polymerization 11.04.5. Conclusions References 11.05 Calcium, Strontium and Barium Complexes in Organic Synthesis Abbreviations 11.05.1. Alkaline-earth metal catalysis: An introduction 11.05.1.1. General background 11.05.1.2. The Schlenk equilibrium: Problems and solutions 11.05.1.3. Historical developments 11.05.1.4. Principles of Ae-mediated catalysis 11.05.2. Hydroamination of unsaturated carbon-carbon bonds 11.05.2.1. Intramolecular hydroamination reactions 11.05.2.2. Asymmetric intramolecular hydroamination reactions 11.05.2.3. Intermolecular hydroamination reactions 11.05.2.3.1. Intermolecular hydroamination of alkenes 11.05.2.3.2. Intermolecular hydroamination of carbodiimides and isocyanates 11.05.2.3.3. Intermolecular hydroamination of alkynes 11.05.2.3.4. Intermolecular hydroamination of diynes 11.05.3. Hydrophosphination and related catalysis 11.05.3.1. Intermolecular hydrophosphination of alkenes 11.05.3.2. Intermolecular hydrophosphination of alkynes 11.05.3.3. Hydrophosphination of carbodiimides 11.05.3.4. Hydrophosphorylation and hydrophosphonylation catalysis 11.05.3.4.1. Hydrophosphorylation of alkynes 11.05.3.4.2. Hydrophosphonylation of aldehydes and ketones 11.05.4. Other hydrofunctionalization reactions with pre-polarized E-H substrates 11.05.4.1. Hydroalkoxylation of alkynyl and allenyl alcohols 11.05.4.2. Hydroacetylenation of carbodiimides and related reactions 11.05.4.3. Hydroboration catalysis 11.05.4.4. Hydrosilylation catalysis 11.05.4.4.1. Hydrosilylation of alkenes 11.05.4.4.2. Hydrosilylation of ketones 11.05.4.4.3. Hydrosilylation of imines 11.05.5. Hydrogenation catalysis 11.05.5.1. Hydrogenation of alkenes 11.05.5.1.1. Hydrogenation of activated alkenes 11.05.5.1.2. Hydrogenation of unactivated alkenes 11.05.5.2. Hydrogenation of imines 11.05.6. Dehydrocoupling catalysis 11.05.6.1. Dehydrocoupling of amines and boranes 11.05.6.1.1. Synthesis of asymmetrical diaminoboranes 11.05.6.1.2. Dehydrocoupling of dimethylamine-borane and tert-butylamine-borane 11.05.6.1.3. Dehydrocoupling of amines and boranes 11.05.6.2. Heterodehydrocoupling of amines and silanes 11.05.6.2.1. Catalyzed NH/HSi heterodehydrocouplings for the formation of mono- and disilazanes 11.05.6.2.1.1. Catalyst selection and substrate scope 11.05.6.2.1.2. Mechanistic insight 11.05.6.2.2. Formation of cyclic disilazanes 11.05.6.2.3. Catalyzed NH/HSi dehydropolymerizations 11.05.6.3. Other alkaline-earth catalyzed heterodehydrocouplings 11.05.6.3.1. Dehydrocouplings of silanes and alcohols 11.05.6.3.2. Dehydrocouplings of silanes and borinic acids 11.05.6.3.3. Dehydrocouplings of silanes and silanols 11.05.6.3.4. Dehydrogenative silylation of activated CH bonds 11.05.7. Miscellaneous catalyzed reactions with reactive [Ae]-X (pre)catalysts 11.05.7.1. Dimerization of aldehydes-Tishchenko reaction 11.05.7.2. Trimerization of isocyanates 11.05.7.3. Alkylation reactions 11.05.7.3.1. Dimerization of terminal alkynes 11.05.7.3.2. Alkylation of aromatic rings 11.05.7.3.3. Alkylation of alkylpyridines 11.05.7.4. Catalyzed H/D exchange 11.05.7.5. Polymerization of ethylene 11.05.7.6. Reduction of carbon-oxygen unsaturated compounds 11.05.7.7. Redistribution and cross-coupling of arylsilanes 11.05.7.8. Reactions other than hydrofunctionalizations and dehydrocouplings 11.05.7.8.1. Desilacoupling of silaboranes and amines 11.05.7.8.2. Cyanosilylation of carbonyls 11.05.7.8.3. Alumination of Csp2H bonds 11.05.8. Alkaline-earth mediated Lewis-acid catalysis 11.05.8.1. Introduction 11.05.8.1.1. Lewis acidity of the group 2 metal cations 11.05.8.1.2. Measuring Lewis acidity 11.05.8.2. Lewis acid catalyzed transformations: CC bond forming reactions 11.05.8.2.1. Mannich reactions 11.05.8.2.2. Cycloaddition reactions 11.05.8.2.2.1. [3+2] cycloadditions 11.05.8.2.2.2. [4+2] cycloadditions 11.05.8.2.3. Chiral 1,4-addition reactions 11.05.8.2.4. Hydroarylation of alkenes 11.05.8.2.5. Heterofunctionalization of alkenes 11.05.8.2.6. Cyclic rearrangements 11.05.8.2.6.1. Nazarov cyclisation 11.05.8.2.6.2. Aza-Piancatelli cyclization 11.05.8.2.7. Ca2+-catalyzed dehydroxylation reactions 11.05.9. In lieu of a conclusion Acknowledgment References 11.06 Zinc Reagents in Organic Synthesis 11.06.1. Introduction 11.06.2. Preparation of organozinc compounds 11.06.2.1. Synthetic routes to prepare homometallic zinc reagents 11.06.2.1.1. Direct insertion of zinc into metal-halogen bonds 11.06.2.1.2. Advances in directed metalation 11.06.2.1.3. Transmetalation routes to prepare organozinc complexes 11.06.2.1.4. Metal-halogen exchange routes to organozinc reagents 11.06.2.2. Preparation of heterometallic compounds 11.06.2.2.1. Co-complexation preparation routes toward heterometallic zincates 11.06.2.2.2. Formation of heterometallic complexes via trans-metal trapping 11.06.3. Applications of organozinc reagents in addition reactions 11.06.3.1. Overview 11.06.3.2. Addition to carbonyl compounds 11.06.3.2.1. Alkylation of carbonyl compounds 11.06.3.2.2. Alkenylation (vinylation) of carbonyls 11.06.3.2.3. Alkynylation of carbonyls 11.06.3.2.4. Arylation of carbonyls 11.06.3.3. Conjugate 1,4-addition to α,β-unsaturated compounds 11.06.3.4. Addition to carbon dioxide 11.06.3.5. Addition to imines 11.06.3.6. Addition to oxabicyclic alkenes 11.06.3.7. Chelation-controlled additions 11.06.3.8. Tandem reactions using organozinc reagents 11.06.3.9. Summary 11.06.4. Applications of organozinc reagents in substitution reactions 11.06.4.1. Overview 11.06.4.2. Asymmetric allylic substitutions 11.06.4.3. Alkylations 11.06.4.4. Alkenylation reactions 11.06.4.5. rylation reactions 11.06.4.6. Summary 11.06.5. Application of organozinc reagents in cross-coupling reactions 11.06.5.1. Overview 11.06.5.2. Negishi cross-coupling reactions 11.06.5.3. Synthesis of functionalized ketones 11.06.5.4. Barbier reactions 11.06.5.5. Summary 11.06.6. Catalytic applications using organozinc reagents 11.06.6.1. Overview 11.06.6.2. Hydrosilylation and dehydrogenative silylation 11.06.6.3. Zinc-catalyzed hydroboration and borylation reactions 11.06.6.4. Zinc-catalyzed hydroamination reactions 11.06.6.5. Summary 11.06.7. Reactivity of molecular zinc hydrides 11.06.7.1. Overview 11.06.7.2. Insertion of unsaturated substrates into ZnH bonds 11.06.7.3. Hydrosilylation reactions 11.06.7.4. Dehydrocoupling of alcohols and silanes 11.06.7.5. Borylation and hydroboration of terminal alkynes 11.06.7.6. Hydrogenation of imines 11.06.7.7. Summary 11.06.8. Reactivity and applications of N-heterocyclic carbene zinc complexes 11.06.8.1. Overview 11.06.8.2. Hydrosilylation of CO2 using NHC-Zn-alkyl complexes 11.06.8.3. Hydroamination of carbodiimides using NHC-Zn-bis(amide) complexes 11.06.8.4. Chiral NHC-Zn-alkyl catalysts for enantioselective allylic alkylations 11.06.8.5. Summary 11.06.9. Organozinc pivalates as enhanced air- and moisture-stability reagents 11.06.9.1. Overview 11.06.9.2. The application of zinc-pivalates in cross-coupling reactions 11.06.9.3. Application of organozinc pivalates in acylations, allylations and carbocuprations 11.06.9.4. Summary 11.06.10. Reactivity of heterometallic organozinc compounds 11.06.10.1. Overview 11.06.10.2. Deprotonative metalation 11.06.10.3. Metal-halogen exchange using heterometallic zincate reagents 11.06.10.4. Addition reactions 11.06.10.5. Silylzincation reactions 11.06.10.6. Cross-coupling reactions 11.06.10.7. Summary 11.06.11. Conclusions Acknowledgment References 11.07 Boron Complexes in Organic Synthesis 11.07.1. General introduction 11.07.2. Boronic acid catalysis 11.07.2.1. Introduction 11.07.2.2. Electrophilic activation 11.07.2.3. Nucleophilic activation 11.07.2.4. Boron-based chiral Brønsted acid catalysts 11.07.3. Transition metal-catalyzed methods 11.07.3.1. Introduction 11.07.3.2. Transition metal-catalyzed cross-coupling 11.07.3.3. Combining transition metal catalysis with metalate rearrangements 11.07.3.4. Photoredox-based methods 11.07.3.4.1. Dual-catalyzed photoredox cross-coupling of alkyltrifluoroborates 11.07.3.4.2. Photoredox activation of boronic acid and esters for C(sp2)C(sp3) cross-coupling 11.07.4. Transition metal-free methods 11.07.4.1. Introduction 11.07.4.2. Transition metal-free borylation 11.07.4.3. Transition metal-free cross-coupling 11.07.4.4. Developments and applications in 1,2-metalate rearrangements 11.07.4.5. Metal-free photoredox processes 11.07.5. Synthetic applications of boronate and boryl anions 11.07.5.1. Introduction 11.07.5.2. Boronate anions 11.07.5.3. Boryl anions 11.07.5.3.1. Formation and examples 11.07.5.3.2. Synthetic applications 11.07.6. Summary Acknowledgment References 11.08 Aluminum Complexes in Organic Synthesis 11.08.1. Introduction 11.08.2. Reduction reactions 11.08.2.1. Reduction of carbonyl compounds: Aldehydes, ketones, esters and amides 11.08.2.1.1. Meerwein-Ponndorf-Verley (MPV) reduction 11.08.2.1.2. Hydroboration 11.08.2.1.3. Hydrosilylation 11.08.2.1.4. Cyanation reactions 11.08.2.1.5. Hydrophosphonylation reactions 11.08.2.1.6. Tishchenko reactions 11.08.2.2. Reduction of carbon dioxide 11.08.2.2.1. Formation of cyclic carbonates 11.08.2.2.2. Formation of methanol equivalents and/or methane 11.08.2.2.2.1. Hydroboration 11.08.2.2.2.2. Hydrosilylation 11.08.2.3. Reduction of alkenes and alkynes 11.08.2.3.1. Hydroboration 11.08.2.3.2. Hydrosilylation 11.08.2.3.3. Hydrophosphination 11.08.2.3.4. Hydroamination 11.08.2.4. Reduction of unsaturated C-N fragments: Imines, carbodiimides, nitriles 11.08.2.4.1. Hydroboration 11.08.2.4.2. Hydrosilylation 11.08.2.4.3. Hydrogenation 11.08.2.4.4. Hydrophosphonylation and hydrophosphination reactions 11.08.2.4.5. Hydroamination 11.08.3. Oxidation reactions 11.08.3.1. Oppenauer oxidation 11.08.3.2. Oxidations with hydrogen peroxide 11.08.3.3. Oxidations with complexes bearing non-innocent ligands 11.08.4. Addition reactions 11.08.4.1. Conjugate additions 11.08.4.2. Mukaiyama aldol reactions 11.08.4.3. Passerini reactions 11.08.5. Cyclization reactions 11.08.5.1. Diels-Alder reactions 11.08.5.2. Passerini-type reactions 11.08.5.3. Intramolecular Prins reactions 11.08.5.4. Ring-closing metathesis 11.08.6. Miscellaneous reaction 11.08.7. The hidden Brønsted acid (catalysis) conundrum 11.08.8. Conclusion References 11.09 Gallium and Indium Complexes in Organic Synthesis 11.09.1. Introduction 11.09.2. Preparation of organogallium compounds 11.09.2.1. Oxidative addition of organic halides 11.09.2.2. Transmetalation 11.09.3. Gallium complexes in organic synthesis 11.09.3.1. Allylation reactions 11.09.3.1.1. Diastereoselective allylation of aldehydes 11.09.3.2. Alkenylation reactions 11.09.3.3. Ethynylation reactions 11.09.3.4. Addition to carbonyl compounds 11.09.3.4.1. Reductive lactonization of γ-keto acids 11.09.3.4.2. Synthesis of gem-diacetates 11.09.3.4.3. Stereoselective synthesis of E-configured α,β-unsaturated ketones 11.09.3.4.4. Deoxygenation of aryl ketones 11.09.3.4.5. Carbonyl-olefin ring closing reactions 11.09.3.4.6. Transition metal-free synthesis of nitriles 11.09.3.4.7. Chloroacylation of alkynes 11.09.3.4.8. Skeletal-α,α,α-trisubstituted aldehyde rearrangement 11.09.3.5. Carbogallation reactions 11.09.3.6. Reduction reactions 11.09.3.7. Coupling reactions 11.09.3.8. Cycloaddition reactions 11.09.3.9. Cycloisomerization reactions 11.09.3.10. Insertion reactions 11.09.3.10.1. Use as Lewis acids and bases 11.09.3.11. Miscellaneous 11.09.3.11.1. Synthesis of 4-halotetrahydropyrans 11.09.3.11.2. Disulfidation of alkynes and alkenes 11.09.3.11.3. Annulation reactions 11.09.3.11.4. Hydroamination reaction 11.09.3.11.5. Ring opening of epoxides 11.09.3.11.6. Biginelli reaction under solvent-free conditions 11.09.3.11.7. Catalytic applications of [IPr.GaX2][SbF6] and associated species 11.09.3.11.8. Activation of alkynyl glycosides 11.09.3.11.9. Consecutive addition using silyl cyanide 11.09.3.11.10. Direct chlorination of alcohols 11.09.3.11.11. Microwave-assisted reaction 11.09.3.11.12. Redox-active reactions 11.09.4. Preparation of organoindium complexes 11.09.5. Indium complexes in organic synthesis 11.09.5.1. Allylation 11.09.5.1.1. Addition to carbonyl compounds and its derivatives 11.09.5.1.1.1. Diastereoselective allylation reactions 11.09.5.1.1.2. Enantioselective allylation reactions 11.09.5.1.2. Allylation of imines 11.09.5.1.2.1. Allylation of imines and their derivatives 11.09.5.1.2.2. Diastereoselectivity in imines 11.09.5.1.2.3. Enantioselectivity in imines 11.09.5.2. Propargylation and allenylation reactions 11.09.5.3. Additions to alkenes and alkynes 11.09.5.4. Indium based carbo- and heterocyclization reactions 11.09.5.4.1. Carbocyclization 11.09.5.4.2. Heterocyclization of oxygen based functional groups 11.09.5.4.3. Heterocyclization of nitrogen based functional groups 11.09.5.5. Coupling reactions 11.09.5.6. Reduction reactions 11.09.5.6.1. Reduction of carbonyl compounds and their derivatives 11.09.5.6.2. Reduction of nitrogen-, oxygen- and other heteroatom containing functional groups 11.09.5.7. Annulation reactions 11.09.5.8. Cycloaddition reactions using indium(III) salts 11.09.5.9. Reactions involving transition metals and chalcogens 11.09.6. Miscellaneous reactions 11.09.6.1. Cycloisomerization reactions 11.09.6.2. Glycosylation reactions 11.09.6.3. Hydroarylation reactions 11.09.6.4. Silylation reactions 11.09.6.5. Redox-active reactions 11.09.7. Conclusion Acknowledgment References 11.10 Silicon and Germanium Complexes in Organic Synthesis 11.11 Tin and Lead in Organic Synthesis 11.11.1. Introduction 11.11.2. `Classical tin chemistry and toxicity 11.11.2.1. Progress regarding polymer-supported tin reagents 11.11.3. Progress in low-valent lead and tin chemistry 11.11.3.1. Tin(I) and lead(I) dimers (distannynes and diplumbynes) 11.11.3.1.1. Alkenes 11.11.3.1.2. Unsaturated nitrogen-nitrogen bonds 11.11.3.1.3. Isocyanides 11.11.3.1.4. Dihydrogen 11.11.3.2. Monomeric tin(II) and lead(II) species (stannylenes and plumbylenes) 11.11.3.2.1. Early work 11.11.3.2.2. Frontier orbitals 11.11.3.2.3. Oxidative addition and reductive elimination reactions of stannylenes and plumbylenes 11.11.3.2.4. Insertion reactions of stannylenes and plumbylenes 11.11.3.2.5. Catalysis promoted by stannylenes 11.11.3.3. Dimeric tin(II) and lead(II) species (distannenes and plumbenes) 11.11.3.3.1. Alkynes 11.11.3.3.2. Phosphalkynes References 11.12 Antimony and Bismuth Complexes in Organic Synthesis 11.12.1. Introduction 11.12.2. Antimony in organic synthesis 11.12.2.1. Organoantimony(I) compounds 11.12.2.2. Organoantimony(II) compounds 11.12.2.3. Organoantimony(III) compounds 11.12.2.3.1. CC Bond forming reactions 11.12.2.3.1.1. Indole additions 11.12.2.3.1.2. Nucleophilic allylations 11.12.2.3.1.3. Friedel-crafts additions 11.12.2.3.1.4. Miscellaneous CC bond forming reactions 11.12.2.3.2. C-X bond forming reactions (X=O, N) 11.12.2.3.3. Reactions involving transition metals 11.12.2.3.4. Multicomponent reactions 11.12.2.3.5. Oxidations 11.12.2.3.6. Reductions 11.12.2.4. Organoantimony(V) compounds 11.12.2.4.1. CC bond forming reactions 11.12.2.4.2. C-X bond formation (X=O, N, S, P) 11.12.2.4.3. Oxidations 11.12.2.4.4. Reductions 11.12.3. Bismuth in organic synthesis 11.12.3.1. Organobismuth(I) compounds 11.12.3.2. Organobismuth(II) compounds 11.12.3.2.1. Ring opening 11.12.3.2.2. Olefin radical polymerization 11.12.3.2.3. Intramolecular CC coupling 11.12.3.2.4. Intermolecular CC coupling 11.12.3.3. Organobismuth(III) compounds 11.12.3.3.1. CC bond forming reactions 11.12.3.3.1.1. Intramolecular cyclizations 11.12.3.3.1.2. Mukaiyama-aldol reaction 11.12.3.3.1.3. Nucleophilic allylations 11.12.3.3.2. C-X (X=O, N, S) bond forming reactions 11.12.3.3.3. Reactions involving transition metals 11.12.3.3.4. Multi-component reactions 11.12.3.3.5. Oxidations 11.12.3.3.6. Reductions 11.12.3.4. Organobismuth(V) compounds 11.12.3.4.1. Stoichiometric C-C/N/O bond formation 11.12.3.4.2. Catalytic CC/N/O bond formation Acknowledgment References 11.13 Selenium and Tellurium Complexes in Organic Synthesis 11.13.1. General introduction 11.13.1.1. Electrophilic selenium and tellurium reagents 11.13.2. Nucleophilic selenium and tellurium reagents 11.13.2.1. Cadmium 11.13.2.2. Lanthanum 11.13.2.3. Indium 11.13.2.4. Samarium 11.13.2.5. Tin 11.13.2.6. Zinc 11.13.2.6.1. Synthesis and reactivity of [RSeZnSeR] generated by oxidative insertion of elemental zinc into the SeSe bond 11.13.2.6.1.1. Oxidative insertion catalyzed by Lewis acids 11.13.2.6.1.2. Oxidative insertion using a recyclable biphasic acidic system 11.13.2.6.2. Synthesis and reactivity of bench stable zinc selenolates (Santi's reagents) 11.13.3. New insights in organoselenium and organotellurium catalysts 11.13.4. Conclusion References 11.14 Frustrated Lewis Pairs in Organic Synthesis 11.14.1. Introduction to frustrated Lewis pairs (FLPs) 11.14.2. FLP-mediated catalytic hydrogenation 11.14.2.1. Early examples of FLP-mediated hydrogenation 11.14.2.2. Substrates which are the Lewis Basic component of FLPs 11.14.3. Air and moisture stable frustrated Lewis pairs 11.14.4. Asymmetric catalysts 11.14.4.1. Enantioselective reduction of CN multiple bonds and silyl enols 11.14.4.2. Hydrosilylation 11.14.4.3. Asymmetric FLP-mediated hydrosilylation 11.14.5. Other FLP-mediated organic transformations 11.14.5.1. FLP-mediated hydroamination 11.14.5.2. FLP-mediated direct Mannich-type reactions 11.14.5.3. FLP-mediated C-H borylation 11.14.5.4. FLP-mediated cyclization reactions 11.14.6. Frustrated radical pairs in organic synthesis 11.14.6.1. FRP-mediated CC bond formations 11.14.7. Summary and outlook References 11.15 Synergistic Effects of Multimetallic Main Group Complexes in Organic Synthesis 11.15.1. Introduction 11.15.2. General properties 11.15.2.1. Enhanced reactivity 11.15.2.2. Enhanced stability 11.15.2.3. Enhanced solubility 11.15.2.4. Cooperative activation 11.15.2.5. Structural templating 11.15.3. Nucleophilic addition reactions 11.15.4. Deprotonative metalation reactions 11.15.5. Catalytic enantioselective reactions 11.15.6. Catalytic hydroamination reactions 11.15.7. Catalytic hydroboration reactions 11.15.8. Catalytic hydrogenation reactions 11.15.9. Catalytic CC bond formation reactions 11.15.10. Conclusion and outlook Acknowledgment References 11.16 Main Group Complexes in Polymer Synthesis 11.16.1. Scope 11.16.2. Introduction 11.16.3. Ring opening polymerization 11.16.3.1. Mechanisms 11.16.3.1.1. Cationic ROP mechanism 11.16.3.1.2. Activated monomer mechanism 11.16.3.1.3. Coordination-insertion ROP mechanism 11.16.3.1.4. Nucleophilic activation mechanism 11.16.3.1.5. Anionic ROP 11.16.4. Polymers accessible by main group catalyzed ROP 11.16.4.1. Polymers derived from cyclic ethers and thioethers 11.16.4.1.1. Polyethers derived from epoxides, O(CH2CHR) 11.16.4.1.2. Higher polyethers derived from cyclic esters, O(CH2)n (n=3, 4) 11.16.4.1.3. Polymers derived from thioethers 11.16.4.2. Polymers derived from cyclic esters, thioesters, and amides 11.16.4.2.1. Polymers derived from lactones 11.16.4.2.1.1. Poly(lactic acid) 11.16.4.2.2. Polymers derived from thiolactones 11.16.4.2.3. Polymers derived from lactams 11.16.4.3. Polymers derived from cyclic carbonates and thiocarbonates 11.16.4.3.1. Polymers derived from cyclic carbonates 11.16.4.3.2. Polymers derived from cyclic thiocarbonates 11.16.5. Ring-opening copolymerization mediated by main group complexes 11.16.5.1. Epoxide/Anhydride ROCOP 11.16.5.2. Epoxide/Heterocumulene ROCOP 11.16.6. Chemical polymer recycling 11.16.6.1. Chemical depolymerization of PLA 11.16.6.2. Chemical degradation of PLA 11.16.6.3. Depolymerization of other polyesters 11.16.7. Conclusion Acknowledgment References Cover back