Polar Organometallic Reagents

1 Cover

2 Title Page

3 Copyright Page

4 Preface

5 List of Contributors

6 Acknowledgements

7 1 The Road to Aromatic Functionalization by Mixed‐metal Ate Chemistry 1.1 Introduction 1.2 Deprotonation of Aromatics 1.3 Aromatic Ate Complex Chemistry: Metal/Halogen Exchange 1.4 Deprotonation Using Ate Complexes 1.5 Concluding Remarks References

8 2 Structural Evidence for Synergistic Bimetallic Main Group Bases 2.1 General Introduction 2.2 Homometallic Bases 2.3 Heterometallic Bases 2.4 Outlook References

9 3 Turbo Charging Group 2 Reagents for Metathesis, Metalation, and Catalysis 3.1 Introduction and Historical Context: Monometallic s‐block Reagents and Their Utility 3.2 Heterobimetallic Reagents for Selective Metalation 3.3 Homogeneous Catalysis by s‐block Reagents 3.4 Outlook: Turbo Charging the Turbo Reagents and Prospects for Catalysis References

10 4 Mechanisms in Heterobimetallic Reactivity 4.1 Introduction and Scope of the Chapter 4.2 Small Molecule Activation and Catalysis 4.3 Polymerization Catalysis 4.4 Conclusion References

11 5 Cationic Compounds of Group 13 Elements 5.1 Introduction 5.2 General Considerations 5.3 Recent Developments in Cationic Group 13 Complexes 5.4 Recent Advancements in Catalytic Applications of Cationic Group 13 Complexes 5.5 Concluding Remarks References

12 6 Recent Development in the Solution Structural Chemistry of Main Group Organometallics 6.1 Introduction 6.2 Monometallic Systems 6.3 Heteropolymetallic Systems 6.4 Concluding Remarks References

13 7 Chemistry of Boryl Anions 7.1 Introduction 7.2 Boryl Anions as a Salt of Alkali Metals 7.3 Boryl Anions as a Salt of Magnesium, Zinc, and Copper as Relatives of Carbanions 7.4 Application of Borylcopper and Borylzinc Species for Synthetic Organic Chemistry 7.5 Summary References

14 8 Novel Chemical Transformations in Organic Synthesis with Ate Complexes 8.1 Introduction 8.2 Ate Complexes 8.3 Di‐anion‐type Zincate 8.4 Heteroleptic Zinc Ate Complexes 8.5 Conclusion References

15 9 Isolable Alkenylcopper Compounds 9.1 Introduction 9.2 Well‐defined Alkenylcopper Compounds 9.3 Summary References

16 Index

17 End User License Agreement

1 Chapter 2 Table 2.1 Effect of identity of alkali metal alkoxide on yield and meta / par ...

2 Chapter 4Table 4.1 Comparison of calculated parameters for 12′and 12′ M...

3 Chapter 5Table 5.1 Perturbation in 31P NMR signal for Gutmann–Beckett Lewis acidity ...Table 5.2 Fluoride ion, chloride ion, and hydride ion affinity (in kJ/mol) ...

4 Chapter 6Table 6.1 Aromatic chemical shifts in the 1H NMR spectra of the products of...Table 6.2 Estimated M rfrom ICC DOSY NMR (expressed in g/mol) for all reas...

5 Chapter 8Table 8.1 Metalation using di‐anion‐type zincate: Li 2[Zn(X)Me 3].Table 8.2 Li 2[Zn t ‐Bu 4] for nucleophilic substitution of propargyl bromide....Table 8.3 Anionic polymerization of N ‐isopropylacrylamide using Li 2[Zn t ‐Bu 4Table 8.4 Regioselective generation of functionalized benzynes with Li[(TMP...

1 Chapter 1 Figure 1.1 The general principles demonstrated by (a) a heterobimetallic ate... Scheme 1.1 A generic directed ortho ‐deprotometalation strategy incorporating... Scheme 1.2 Representation of a generic directed ortho ‐lithiation strategy. Scheme 1.3 Steric effects on the directed ortho ‐lithiation of aromatic ester... Figure 1.2 Dimer structures of (a) i ‐Pr 2NC(O)‐2‐Et‐C 6H 3Li(THF) 5and (b) hem... Scheme 1.4 The rearrangement of [2‐(Me 2NCH 2)C 10H 6Li‐1] 2(dman) 9in hot tolue... Scheme 1.5 Selective magnesiation of an alkyl benzoate using magnesium amide... Scheme 1.6 Treatment of methyl 1‐phenylsulfonylindole‐3‐carboxylate with ( i ‐... Scheme 1.7 Ortho ‐magnesiation of a borylbenzene via internal reaction of N ‐m... Figure 1.3 Structure of the ortho C , N ‐magnesiated dimer of 25( 12). Scheme 1.8 The use of ( DipNacnac)MgTMP 27in pyrazine deprotometalation. Figure 1.4 Molecular structures of (a) [{PhN(H)} 2( t ‐BuO)LiNaK(TMEDA) 2] 2 31 2a... Scheme 1.9 Reactivity of metal alkoxides towards toluene in C 5D 5N. L = η 6: ... Figure 1.5 Molecular structure of [{4,6‐Me 2C 6H 2(O)(CH 2)}LiNa(TMEDA)] 4 34 4.... Figure 1.6 Molecular structure of the core of (PhK) 4(PhLi)( t ‐BuOLi)(THF) 6(C 6 Figure 1.7 Molecular structures of (a) Li 4K 4Np 2.75( t ‐BuO) 5.25 36and (b) Li 4K Figure 1.8 Molecular structure of [Li 4KNp 2(O t ‐Bu) 3] 2 38 2(K = dark purple, Li... Scheme 1.10 The elaboration of ferrocene employing 39. Fc = ferrocenyl, n = ... Scheme 1.11 Reactions of TMPMgCl(LiCl) 41with 5‐bromopyrimidine (top) and a... Scheme 1.12 Ortho ‐magnesiation by TMP 2Mg(LiCl) 2 44 TMPof an aromatic bis(dim... Scheme 1.13 Halogen–zinc exchange in a para ‐substituted aromatic iodide. Scheme 1.14 Use of a lithium zincate to avoid intermediate rearrangement of ... Scheme 1.15 The contrasting reactivity of an allyl 2‐iodophenyl ether with M... Scheme 1.16 Investigation of the migratory aptitude of lithium dialkylphenyl... Scheme 1.17 Tert ‐butyl as a nontransfer group; 65incurs the halogen–zinc ex... Scheme 1.18 Treatment of methyl 4‐iodobenzoate with 65preceded allylation (... Scheme 1.19 Addition reaction involving the transmetalation of putative lith... Figure 1.9 Molecular structures of (a) solvated (DMBA) 3ZnLi 76and (b) (DMBA... Scheme 1.20 Competing SIP and CIP formation in Me 3ZnLi chemistry. Scheme 1.21 Halogen–metal exchange of p ‐iodoanisole with cuprate 81at −78 °... Scheme 1.22 Reaction of methyl p ‐iodobenzoate and 81, with subsequent oxidat... Scheme 1.23 The contrasting reactivity of an epoxide with n ‐BuLi and differe... Figure 1.10 Structures of phosphine‐stabilized (a) CIP [Me 2Cu][Cu(PPh 3)] or ... Scheme 1.24 Synthesis of lithium dimethylcuprate 83. Figure 1.11 Structures of phenylcuprate species (a) [Ph 6Cu 3Li 2] −in 98 Figure 1.12 Selected higher‐order cuprates (a) Ph 5Cu 2Li 3(SMe 2) 4 101and (b) ... Figure 1.13 Molecular structures of the dimers of (a) (DMBA) 2CuLi 103and (b... Figure 1.14 Structures of (a) SIP [{(Me 3Si) 3C} 2Cu][Li(THF) 4] 106, and (b) be... Figure 1.15 Molecular structure of [C 6H 4{CH 2N(Me)CH 2CH 2NMe 2}‐2] 2Cu(Br)Li 2 112 Figure 1.16 Molecular structures of (a) polymeric (DMBA) 2Cu(CN)Li 2(THF) 4 114,... Scheme 1.25 Use of ate complex t ‐Bu 3ZnLi 65as a solid‐phase metalating agen... Scheme 1.26 Synthesis of t ‐Bu 2Zn(TMP)Li 1. Scheme 1.27 Application of 1in biaryl synthesis. Figure 1.17 Proposed intermediates in the metalation of selected heteroaroma... Figure 1.18 A generalized alkali metal zincate. Scheme 1.28 Transmetalation of lithioanisole to variously solvated ortho ‐zin... Scheme 1.29 The anionic Fries rearrangement and its avoidance using lithium ... Scheme 1.30 Comparing the performance of Cd and Zn reagents in aromatic halo... Scheme 1.31 Synthesis of i ‐Bu 3Al(TMP)Li 144. Scheme 1.32 Ortho ‐alumination of a functionalized aromatic ring. Figure 1.19 Model aluminate