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 Mr from ICC DOSY NMR (expressed in g/mol) for all reas...
5 Chapter 8Table 8.1 Metalation using di‐anion‐type zincate: Li2[Zn(X)Me3].Table 8.2 Li2[Znt‐Bu4] for nucleophilic substitution of propargyl bromide....Table 8.3 Anionic polymerization of N‐isopropylacrylamide using Li2[Znt‐Bu4Table 8.4 Regioselective generation of functionalized benzynes with Li[(TMP...
List of Illustrations
1 Chapter 1Figure 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‐Pr2NC(O)‐2‐Et‐C6H3Li(THF) 5 and (b) hem...Scheme 1.4 The rearrangement of [2‐(Me2NCH2)C10H6Li‐1]2(dman) 9 in 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 orthoC,N‐magnesiated dimer of 25(12).Scheme 1.8 The use of (DipNacnac)MgTMP 27 in pyrazine deprotometalation.Figure 1.4 Molecular structures of (a) [{PhN(H)}2(t‐BuO)LiNaK(TMEDA)2]2312 a...Scheme 1.9 Reactivity of metal alkoxides towards toluene in C5D5N. L = η6 : ...Figure 1.5 Molecular structure of [{4,6‐Me2C6H2(O)(CH2)}LiNa(TMEDA)]4344....Figure 1.6 Molecular structure of the core of (PhK)4(PhLi)(t‐BuOLi)(THF)6(C6Figure 1.7 Molecular structures of (a) Li4K4Np2.75(t‐BuO)5.2536 and (b) Li4KFigure 1.8 Molecular structure of [Li4KNp2(Ot‐Bu)3]2382 (K = dark purple, Li...Scheme 1.10 The elaboration of ferrocene employing 39. Fc = ferrocenyl, n = ...Scheme 1.11 Reactions of TMPMgCl(LiCl) 41 with 5‐bromopyrimidine (top) and a...Scheme 1.12 Ortho‐magnesiation by TMP2Mg(LiCl)244 TMP of 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; 65 incurs the halogen–zinc ex...Scheme 1.18 Treatment of methyl 4‐iodobenzoate with 65 preceded allylation (...Scheme 1.19 Addition reaction involving the transmetalation of putative lith...Figure 1.9 Molecular structures of (a) solvated (DMBA)3ZnLi 76 and (b) (DMBA...Scheme 1.20 Competing SIP and CIP formation in Me3ZnLi chemistry.Scheme 1.21 Halogen–metal exchange of p‐iodoanisole with cuprate 81 at −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 [Me2Cu][Cu(PPh3)] or ...Scheme 1.24 Synthesis of lithium dimethylcuprate 83.Figure 1.11 Structures of phenylcuprate species (a) [Ph6Cu3Li2]− in 98Figure 1.12 Selected higher‐order cuprates (a) Ph5Cu2Li3 (SMe2)4101 and (b) ...Figure 1.13 Molecular structures of the dimers of (a) (DMBA)2CuLi 103 and (b...Figure 1.14 Structures of (a) SIP [{(Me3Si)3C}2Cu][Li(THF)4] 106, and (b) be...Figure 1.15 Molecular structure of [C6H4{CH2N(Me)CH2CH2NMe2}‐2]2Cu(Br)Li2112Figure 1.16 Molecular structures of (a) polymeric (DMBA)2Cu(CN)Li2(THF)4114,...Scheme 1.25 Use of ate complex t‐Bu3ZnLi 65 as a solid‐phase metalating agen...Scheme 1.26 Synthesis oft‐Bu2Zn(TMP)Li 1.Scheme 1.27 Application of 1 in biaryl synthesis.Figure 1.17 Proposed intermediates in the metalation of selected heteroaroma...