Polar Organometallic Reagents. Группа авторов
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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‐Bu3Al(TMP)Li 144.Scheme 1.32 Ortho‐alumination of a functionalized aromatic ring.Figure 1.19 Model aluminate 149, obtained by sequentially treating ArC(O)Ni‐...Scheme 1.33 i‐Bu2Al(TMP)2Li 150 has enabled the conversion of 4‐halo‐a...Figure 1.20 Molecular structures of aluminated precursors 154 and 155 to (a)...Figure 1.21 Representation of the Gilman amidocuprate (TMP)2CuLi.Scheme 1.34 A generalized view of directed ortho‐cupration.Figure 1.22 Molecular structure of Lipshutz cuprate dimer [(TMP)2Cu(CN)Li2(T...Figure 1.23 Molecular structures of organoamidocuprates (a) [MesCu(NBn2)Li]2Scheme 1.35 Selective formation of Gilman and Lipshutz‐type cuprates from Cu...Figure 1.24 Molecular structures of (a) Gilman amidocuprate dimer of (TMP)2C...Figure 1.25 (a) Schematic of an adduct cuprate structure‐type and (b) molecu...Figure 1.26 Molecular structures of heteroleptic cuprates (a) [(TMP)(DMP)Cu(...Figure 1.27 Molecular structures of the dimers of thiocyananto(amido)cuprate...Figure 1.28 Examples of cyanatocuprates (a) [(TMP)2Cu(OCN)Li2(THF)]21722 and...Figure 1.29 Isomers of (TMP)4Cu2Li2; (a) dimer of conventional Gilman cuprat...Figure 1.30 Structurally characterized organoamidocuprate aggregates (a) Ph(...Figure 1.31 The dimer of lithium argentate (TMP)2Ag(CN)Li2(THF) 179.Scheme 1.36 Examples of directed deprotometalation using lithium argentate 1...Figure 1.32 Molecular structure of the dimer of [2‐(i‐Pr)2NC(O)‐C6H4]2AgLi(T...Scheme 1.37 Lithium argentate 179 shows good functional group tolerance when...
2 Chapter 2Figure 2.1 Common oligomeric structures adopted by the organolithium reagent...Figure 2.2 Part of the infinite solid‐state ladder structure of PhLi 2.Scheme 2.1 Disruption of the polymerization of MeLi tetramers 1 by common Le...Figure 2.3 Molecular structures of n‐BuLi 7 (left) and t‐BuLi 8 ...Scheme 2.2 Disruption of the n‐BuLi hexamer by polydentate Lewis donor...Scheme 2.3 Deprotonation of PMDETA by coordinated n‐BuLi producing 16....Figure 2.4 Distortion to the central Li2C2 rings of dimeric t‐BuLi and...Scheme 2.4 Donor dependence of n‐BuLi reactivity towards benzene and t...Scheme 2.5 Contrasting solvent‐dependent reactivity of BuLi with the heteroc...Figure 2.5 Polymeric structures of trimethylsilylmethylsodium 24 (top) and b...Scheme 2.6 Effect of TMEDA on structures of trimethylsilylmethylsodium and b...Figure 2.6 Common secondary amines employed for metallation chemistry.Scheme 2.7 Simplified bonding in metal‐amide oligomers, using a cyclodimer a...Figure 2.7 Molecular structures of LiDA 35, LiHMDS 36, and LiTMP 37a/37b....Figure 2.8 Representative example of higher‐order and lower‐order structures...Figure 2.9 Influence of the agostic interactions on homo‐, hetero‐ and solva...Figure 2.10 LiCKOR metallation of toluene.Scheme 2.8 Lithiation of sodium 2,4,6‐trimethylphenoxide to yield the hetero...Figure 2.11 Molecular structure of trimetallic alkoxide complex 59 (K = dark...Scheme 2.9 Contrasting reactivity of LiCKOR superbase in the presence and ab...Figure 2.12 Molecular structures of [(THF)2Li(μ‐Cl)2Mg(THF)TMP] 60 (left) an...Scheme 2.10 Synthesis of heteroleptic sodium zincate 62 by metallation of be...Scheme 2.11 Contrasting reactivity of a homometallic zinc reagent and a bime...Scheme 2.12 Contrasting reactivity of homoleptic bimetallic HMDS complexes w...Scheme 2.13 Proposed mechanism of addition of diarylmethanes to alkenes cata...Scheme 2.14 Examples of the metallation scope of LiZnt‐Bu2(TMP).Figure 2.13 Molecular structure of [(THF)Li(TMP)(t‐Bu)Zn(t‐Bu)] Scheme 2.15 Computed transition states for addition versus metallation react...Scheme 2.16 Stoichiometry dependent variable reactivity of LiZn(t‐Bu)2(TMP) ...Scheme 2.17 Two‐step mechanism of substrate deprotonation with mixed amido/a...Scheme 2.18 Experimental evidence for alkyl dependence upon two‐step mechani...Scheme 2.19 Disproportionation of anisolyl lithium zincate and the molecular...Figure 2.14 Propagation of EtZn(Et)(TMP)Li 75 into a polymer.Scheme 2.20 Synthetic approach and molecular structures of [EtZn{C10H6C(=O)NFigure 2.15 Molecular structures of [{(C5H5)Fe(C5H4)}2Zn(TMEDA)] 79 (left) a...Scheme 2.21 Cascade of reactions upon deprotonating ferrocene with dialkyl‐a...Figure 2.16 Molecular structure of [(TMEDA)Na(TMP)(t‐Bu)Zn(t‐Bu)...Scheme 2.22 Stoichiometry dependent mono‐ and di‐deprotonation of aromatic s...Scheme 2.23 Meta‐deprotonation of N,N‐dimethylaniline using sodium TMP–zinca...Figure 2.17 Molecular structure of [(3‐Me‐C6H4CN)2Na(TMEDA)2]+ [{6‐Zn(t‐...Scheme 2.24 Calculated two‐step mechanism for zincation of benzene with bisa...Scheme 2.25 Dimetallation of thiophene to form novel zincocycle 90.Scheme 2.26 Zincation of benzoylferrocene showing metallated intermediate 91Scheme 2.27 Zincation of THF with sodium