Polar Organometallic Reagents. Группа авторов
and transamidation processes...Figure 6.10 Dimeric structures for 2‐MeTHF complexes of 36–38 as established...Scheme 6.8 [PhN=N(C10H6)O]6Mg2Li242, based on two truncated cubes sharing a ...Scheme 6.9 The selective dimagnesiation of un‐ and monosubstituted arenes su...Scheme 6.10 Proposed equilibrium in d12‐cyclohexane solution between sodium...Scheme 6.11 (i) Potential solution structures of 50 in THF (solid‐state stru...Scheme 6.12 (i) Solution behaviour of LiCl‐free DAMgCl 57 in THF, and (ii) t...Scheme 6.13 66(THF)4 has been shown to undergo dismutation in THF to give 67Scheme 6.14 The convoluted equilibrium resulting from the rearrangement of 6...Scheme 6.15 Using lithium amide 23 along with 69 as a TMT agent in the deriv...Figure 6.11 Colour‐coded structure of 72 (left) and selected nOes associated...Scheme 6.16 The effects of order on the addition of the single‐metal compone...Scheme 6.17 Proposal for the reaction of CdCl2 with 23 and a demonstration ...Scheme 6.18 Proposed solution equilibrium between CIP 792 and its SIP form 7...Scheme 6.19 Top, reactions in Et2O at −100 °C of RLi (n = 2 or less, R = Me3Scheme 6.20 Rapid injection (RI) synthesis of Cu(III) intermediate 92 using ...Scheme 6.21 Synthesis of Cu(III) intermediate 95 using MeCu(13CN)Li 96.Figure 6.12 Proposed major (left) and minor (right) π‐complexes achieved by ...Figure 6.13 In 100, Sol = d10‐OEt2, which gradually changes to d8‐THF as m...Scheme 6.22 The structural possibilities elucidated for cuprate 102 in hydro...Scheme 6.23 The effect of gradual THF addition to a hydrocarbon solution of Scheme 6.24 Synthesis of 109 and the 7Li NMR spectrum obtained upon dissolvi...Figure 6.14 Depending on their relative populations, heating LTMP 23 and CuT...Scheme 6.25 Synthesis of 112–114 via intermediate 116.Scheme 6.26 Dissociative interchange of Li and TMP in 114, mediated by symme...Scheme 6.27 Proposed two‐step mechanism for AMMZn, in this case of anisole, ...Scheme 6.28 The contrasting reactivities of 118 and 119 towards HTMP in d6 Scheme 6.29 Contrasting outcomes of the AMMZn of fluoromethylbenzene by sodi...Scheme 6.30 Proposed mechanism (from DFT calculations) for the directed meta...Scheme 6.31 Synthesis of heteroleptic, alkoxide‐containing lithium zincates Scheme 6.32 Concentration‐dependent, dynamic equilibrium of 133 with its mon...Scheme 6.33 A temperature‐dependent equilibrium process affecting 135 in THF...
7 Chapter 7Scheme 7.1 Reports of nucleophilic boron compounds prior to boryllithium [Di...Scheme 7.2 Synthesis of boryllithium 4 and its reaction with water.Figure 7.1 Crystal structures of (4·DME)2 and 4·(THF)2.Scheme 7.3 Reactivity of boryllithium 4 as a boron nucleophile.Scheme 7.4 (a) Generation of boryl anion 8 as an ate complex of lithium in a...Figure 7.2 Crystal structure of 8.Scheme 7.5 Synthesis and reactivity of 1,2,4,3‐triazaborol‐3‐yllithium 9.Scheme 7.6 Synthesis and reactivity of NHC‐stabilized borole anion 10 (Mes =...Scheme 7.7 Synthesis and reactivity of NHC‐stabilized parent boryl anion 11....Scheme 7.8 Synthesis and reactivity of cAAC‐stabilized parent boryl anion 12Scheme 7.9 Synthesis and reactivity of cyanide‐stabilized λ 3‐tricyanob...Scheme 7.10 Synthesis and reactivity of cAAC‐stabilized dicyanoboryl anion 1...Scheme 7.11 Synthesis and reactivity of NHC‐stabilized dicyanoboryl anion 15Scheme 7.12 Linear dimetalloborylene complex 16 having a nucleophilicity on ...Scheme 7.13 Synthesis and reactivity of borylmagnesium.Scheme 7.14 Generation of borylcopper and borylzinc species from boryllithiu...Scheme 7.15 Generation of borylmagnesium and borylzinc species 9 from 1,2,4,...Scheme 7.16 Generation of borylzinc species from boryllithium 21 and subsequ...Scheme 7.17 Nucleophilic borylation of boron compounds by using boryllithium...Scheme 7.18 Reaction of boryllithium 4 with amino(dibromo)pnictogen [Ar = 2,...Scheme 7.19 Generation of borylmagnesium species by transmetalation of B2pinScheme 7.20 Reactivity of 41 and 42.Scheme 7.21 Zinc‐catalyzed borylation of aryl halide involving borylzincate Scheme 7.22 Generation of boryl(cyano)cuprate 52 and subsequent reaction wit...Scheme 7.23 Direct carboboration of 1‐phenylpropyne derivatives by using bor...Scheme 7.24 Pd‐catalyzed coupling of borylzinc 58 with bromoarenes and acid ...
8 Chapter 8Figure 8.1 Zinc ate complexes.Scheme 8.1 Halogen–zinc exchange reaction of aryl iodides with Li[ZnMe3].Scheme 8.2 Enhanced reactivity of di‐anion‐type zincate.Scheme 8.3 Li2[Znt‐Bu4]: proton‐proof metalating agent.Scheme 8.4 Negishi‐type cross‐coupling reaction via C–O bond cleavage.Figure 8.2 Heteroleptic zincates: an enormous range of possibilities.Scheme 8.5 Highly regio‐ and chemoselective zincation of (hetero)aromatics....Scheme 8.6 Ortho‐iodination of bromobenzenes without benzyne formation.Scheme 8.7 Chemoselective deprotonative ortho‐alumination with Li[(TMP)Ali‐B...Scheme 8.8 Directed ortho‐cupration with Li2[(TMP)Cu(CN)Me].Scheme 8.9 Arylcuprate reactivity.Scheme 8.10 Amidocuprate hydroxylation of aromatics.Scheme 8.11 DFT calculations (kcal/mol) to assess the reaction mechanism for...Scheme 8.12 Amidocuprate amination of aromatics.Scheme 8.13 Reduction of carbonyl compounds with M[HZnMe2].Scheme 8.14 Semi‐reduction of carboxylic acids to aldehydes.Scheme 8.15 Direct conversion of carboxylic acids to ketones by zincates.Scheme 8.16 Silylzincation of alkynes with SiBNOL‐Zn‐ate.Scheme 8.17 Silylzincation of alkynes via Si–B bond activation.Scheme 8.18 Silylzincation of alkenes with SiSiNOL‐Zn‐ate catalyzed by Cp2Ti...Scheme 8.19 CuCN‐catalyzed silylzincation of alkenes.Figure 8.3 Decomposition of RF‐organometallics.Scheme 8.20 Zincation of perfluoroalkyl iodide.Scheme 8.21 Perfluoroalkylation and ‐arylation of carbonyl compounds.Scheme 8.22 Aromatic perfluoroalkylation.Figure 8.4 Model DFT calculation on borylzincate formation M06/SVP (Zn) and ...Figure 8.5 Design of a catalytic boration cycle for aryl halides.Scheme 8.23 Substrate scope of aromatic boration.Scheme 8.24 Borylzincation reaction of benzynes.Figure 8.6 Concept for the trans‐selective boration of triple bonds.Scheme 8.25 Fruitless intermolecular diboration of alkynes.Scheme 8.26 Trans‐selective diboration of alkynes.Scheme 8.27 One‐pot diboration reactions.Scheme 8.28 Sequential diboration/Suzuki–Miyaura cross‐coupling, leading to ...Scheme 8.29 Trans‐alkynylboration of alkynes.Scheme 8.30 Transformation of oxaboroles.
9 Chapter 9Scheme 9.1 Synthesis of 1‐aryl‐propenyl copper compounds with N‐coordination...Scheme 9.2 Synthesis of a mixed alkenyl–aryl copper complex.Scheme 9.3 Synthesis of an alkenylcopper–alkyne π‐complex.Scheme 9.4 Syntheses of mononuclear alkenylcopper–carbene complex.Scheme 9.5 Syntheses of dinuclear alkenylcopper–carbene complexes.Scheme 9.6 Revised mechanism of hydroalkylation of alkynes involving a dicop...Scheme 9.7 Syntheses and transformations of butadienyl and octatetraenyl cop...Scheme 9.8 Reaction of butadienyl 1,4‐dicopper tetramer and octatetraenyl tr...Scheme 9.9 Syntheses of styrenyl and butadienyl copper aggregates from zirco...Scheme 9.10 Formation of aromatic dicupra[10]annulenes.Scheme 9.11 Proposed mechanism for the formation of dicupra[10]annulenes.Scheme 9.12 Syntheses of spiro organocopper(I) compounds and organocopper(II...Scheme 9.13 Reductive elimination of tetra‐carbon‐linked copper(III) complex...Scheme 9.14 Synthesis and oxidation of a butadienyl spiro copper complex.Scheme 9.15 Proposed mechanism of the formation of octatetraenyl copper aggr...Scheme 9.16 Syntheses of rigid magnesium organocuprates and organoargentates...Scheme 9.17 Transformation and preliminary reactivity of magnesium organocup...
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