Читать книгу Computational Methods in Organometallic Catalysis - Yu Lan - Страница 4
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Оглавление1 Chapter 1Scheme 1.1 Cross‐coupling reactions with nucleophiles and electrophiles.Scheme 1.2 Some selected examples of nucleophiles.Scheme 1.3 A brief history of organometallic chemistry.Scheme 1.4 Revealing the reaction mechanism of organometallic catalysis.Scheme 1.5 The resonance structures of (Xantphos)Pd(CH2NBn2)+.Scheme 1.6 Mechanism of rhodium‐catalyzed coupling reaction of quinoline N‐o...Scheme 1.7 Mechanism study of organometallic catalysis by density functional...
2 Chapter 2Scheme 2.1 Jacob's ladder of density functionals.Scheme 2.2 The frequently used approaches for the dispersion correction of d...Scheme 2.3 The combination of Gaussian‐type orbitals (GTOs) for the construc...
3 Chapter 3Scheme 3.1 The coordination of ligand onto metal.Scheme 3.2 Back‐donation bonds in metal‐η2–alkene (a), metal‐η2–dihydrogen (...Figure 3.1 The free‐energy profiles for the coordination of phosphine onto p...Figure 3.2 The free‐energy profiles for the coordination of acetylene onto O...Figure 3.3 The free‐energy profiles for the moving of Cr(CO)3 on a polycycli...Figure 3.4 The relative free energies of Ni–carbene complexes. The free ener...Figure 3.5 The free‐energy profiles for the dissociation of phosphine ligand...Scheme 3.3 Possible pathways for the ligand exchange.Figure 3.6 The mechanism of ligand exchange in the regeneration of Pd‐cataly...Figure 3.7 The free‐energy profiles for the cis‐/trans‐isomerization of Cl2P...Figure 3.8 The free‐energy profiles for the Ni‐shift on the ketene. The ener...Scheme 3.4 Typical oxidative addition.Scheme 3.5 Concerted oxidative addition.Scheme 3.6 (a) The oxidative addition of aryl halide onto Pd(0). (b) The sec...Figure 3.9 The free‐energy profiles for the oxidative addition of aryl chlor...Figure 3.10 The free‐energy profiles for the oxidative addition of ketene on...Figure 3.11 The free‐energy profiles for the oxidative addition of NBS onto ...Scheme 3.7 Oxidative addition through substitutions.Figure 3.12 The free‐energy profiles for the SN2‐substitution‐type oxidative...Figure 3.13 The free‐energy profiles for the SN2‐substitution‐type oxidative...Figure 3.14 The free‐energy profiles for the SNAr‐ substitution‐type oxidati...Figure 3.15 The free‐energy profiles for the oxidative addition of Ni(II) sp...Figure 3.16 The free‐energy profiles for the radical substitution by Ni(I)–c...Figure 3.17 The free‐energy profiles for the oxidative addition of Cu(I) wit...Figure 3.18 The energy profiles for the radical‐type oxidation of Cu(II) by ...Scheme 3.8 Oxidative cyclization.Figure 3.19 The free‐energy profiles for the oxidative cyclization in Pauson...Figure 3.20 The free‐energy profiles for the oxidative cyclization of Ni(0)....Figure 3.21 The free‐energy profiles for the oxidative cyclization of Rh(I)....Scheme 3.9 The isomerization of allene‐coordinated Pd(0). The energies were ...Scheme 3.10 Concerted reductive elimination.Figure 3.22 The free‐energy profiles for the reductive elimination of Pd–div...Figure 3.23 The free‐energy profiles for the reductive elimination of Au–dia...Scheme 3.11 Pd‐catalyzed cross‐coupling reaction of benzyl chlorideand allyl...Scheme 3.12 Reductive elimination through nucleophilic substitution.Figure 3.24 The free‐energy profiles for the substitution‐type reductive eli...Figure 3.25 The energy profiles for the substitution‐type reductive eliminat...Scheme 3.13 Reductive elimination through radical substitution.Figure 3.26 The energy profiles for the reduction of Cu(II) through radical ...Figure 3.27 The energy profiles for the reduction of Cu(II) through intramol...Figure 3.28 The free‐energy profiles for the bimetallic reductive eliminatio...Figure 3.29 The free‐energy profiles for the eliminative reduction of Pd(IV)...Scheme 3.14 Insertion. (a) 1,2‐Insertion, (b) 1,1‐insertion.Figure 3.30 The free‐energy profiles for the 1,2‐alkene insertion in Pd‐cata...Figure 3.31 The free‐energy profiles for the 1,2‐alkyne insertion into Co—C(...Figure 3.32 The free‐energy profiles for the 1,2‐acyl insertion through eith...Figure 3.33 The free‐energy profiles for the 1,1‐carbonyl insertion. The ene...Figure 3.34 The free‐energy profiles for the formation of Rh–carbene complex...Figure 3.35 The free‐energy profiles for the formation of Rh–nitrene complex...Figure 3.36 The free‐energy profiles for the 1,4‐conjugative insertion of di...Figure 3.37 The free‐energy profiles for the carbene insertion. The energies...Figure 3.38 The free‐energy profiles for the acyl insertion through an outer...Scheme 3.15 Elimination. (a) β‐Elimination, (b) α‐elimination.Figure 3.39 The free‐energy profiles for the β‐elimination in Pd‐catalyzed H...Figure 3.40 The free‐energy profiles for the Co‐hydride catalyzed Z‐/E‐isome...Figure 3.41 The free‐energy profiles for the Rh(I) mediated β‐hydride elimin...Figure 3.42 The free‐energy profiles for the Rh(I)‐mediated β‐aryl eliminati...Figure 3.43 The free‐energy profiles for the Rh(I)‐mediated β‐allyl eliminat...Figure 3.44 The free‐energy profiles for the Ru‐mediated β‐carbon eliminatio...Figure 3.45 The free‐energy profiles for the Ni‐mediated β‐amino elimination...Figure 3.46 The free‐energy profiles for the Ni‐mediated α‐aryl elimination....Scheme 3.16 Transmetallation. (a) Metathesis type transmetallation, (b) Subs...Scheme 3.17 Concerted transmetallation.Figure 3.47 The free‐energy profiles for the concerted transmetallation betw...Figure 3.48 The free‐energy profiles for the concerted transmetallation betw...Figure 3.49 The free‐energy profiles for the concerted transmetallation betw...Figure 3.50 The free‐energy profiles for the second transmetallation in Nigi...Figure 3.51 The free‐energy profiles for the alkoxysilane‐catalyzed transmet...Figure 3.52 The free‐energy profiles for the transmetallation in Negishi cou...Figure 3.53 The free‐energy profiles for the transmetallation of nickel brom...Figure 3.54 The free‐energy profiles for the transmetallation of propargyl b...Scheme 3.18 Transmetallation through electrophilic substitution.Figure 3.55 The free‐energy profiles for the transmetallation of rhodium and...Figure 3.56 The free‐energy profiles for the transmetallation of vinyl stann...Figure 3.57 The free‐energy profiles for the transmetallation through oxidat...Scheme 3.19 Metathesis.Scheme 3.20 σ‐bond metathesis and FMO interactions.Figure 3.58 The free‐energy profiles for the σ‐bond metathesis of Zr(IV)(NMeFigure 3.59 The free‐energy profiles for the σ‐bond metathesis of Ni(II) ter...Figure 3.60 The free‐energy profiles for the Rh‐F‐mediated C—H activation th...Scheme 3.21 Olefin metathesis and its mechanism.Scheme 3.22 FMO interactions of olefin metathesis.Figure 3.61 The free‐energy profiles for the Ru‐mediated olefin metathesis. ...Figure 3.62 The free‐energy profiles for the Ru‐mediated olefin/acetylene me...Scheme 3.23 Alkyne metathesis.Figure 3.63 The free‐energy profiles for the Re‐mediated alkyne metathesis. ...
4 Chapter 4Scheme 4.1 A typical catalytic cycle for Ni‐mediated C—H activation and func...Figure 4.1 The free‐energy profiles for the Ni catalyzed C—H activation and ...Figure 4.2 The free‐energy profiles for the Ni catalyzed C—H activation and ...Figure 4.3 The free‐energy profiles for the Ni catalyzed C—H activation and ...Figure 4.4 The free‐energy profiles for the acetylene‐assisted Ni catalyzed ...Figure 4.5 The free‐energy profiles for the Ni‐catalyzed Tishchenko reaction...Scheme 4.2 General catalytic cycles for the Ni‐mediated C—halogen bond activ...Figure 4.6 The free‐energy profiles for the Ni‐catalyzed carbonylation of al...Figure 4.7 The free‐energy profiles for the Ni‐catalyzed trifluoromethylthio...Figure 4.8 The free‐energy profiles for the Ni‐catalyzed cross‐coupling reac...Figure 4.9 The energy profiles for the Ni(I)‐catalyzed Negishi cross‐couplin...Scheme 4.3 Ni‐catalyzed Negishi type cross‐coupling reactions through a radi...Figure 4.10 The free‐energy profiles for Ni‐catalyzed Negishi‐type cross‐cou...Figure 4.11 The free‐energy profiles for Ni‐catalyzed reductive coupling bet...Figure 4.12 The free‐energy profiles for Ni‐catalyzed cross‐coupling reactio...Scheme 4.4 Ni‐mediated C—O bond activation.Figure 4.13 The free‐energy profiles for Ni‐catalyzed catalyzed hydrogenolys...Scheme 4.5 The competition of the oxidative addition with C(aryl)—O bond or ...Figure 4.14 The free‐energy profiles for base‐assisted oxidative addition of...Figure 4.15 The free‐energy profiles for Lewis acid‐assisted oxidative addit...Scheme 4.6 Possible models for Ni(0)‐mediated C—O bond activation.Scheme 4.7 The Ni‐assisted C—O bond activation of phenyl acetate.Figure 4.16 The free‐energy profiles for the Ni‐catalyzed decarboxylative ar...Scheme 4.8 Regioselectivity of Ni‐catalyzed ester arylation.Figure 4.17 The free‐energy profiles for the Ni‐catalyzed regioselective est...Scheme 4.9 Ligand‐controlled regioselectivity of Ni‐catalyzed ester arylatio...Figure 4.18 The free‐energy profiles for the oxidative addition of C—O bond ...Figure 4.19 The free‐energy profiles for the oxidative addition of C—O bond ...Figure 4.20 The free‐energy profiles for the Ni‐mediated deaminative Suzuki–...Figure 4.21 The free‐energy profiles for the Ni‐catalyzed Suzuki–Miyaura cro...Figure 4.22 The free‐energy profiles for the Ni‐catalyzed esterification of ...Figure 4.23 The energy profiles for the Ni‐catalyzed phenylcyanation of alky...Figure 4.24 The free‐energy profiles for the Ni‐catalyzed transfer hydrocyan...Figure 4.25 The free‐energy profiles for the Ni‐assisted decomposition of ke...Scheme 4.10 Ni‐mediated unsaturated bond activation.Scheme 4.11 Mechanism of Ni‐mediated two‐component unsaturated compounds act...Figure 4.26 The energy profiles for the key step of Ni‐mediated enyne cycloa...Figure 4.27 The free‐energy profiles for the key step of Ni‐mediated alkyne–...Figure 4.28 The free‐energy profiles for the Ni(0)‐catalyzed hydroalkoxylati...Figure 4.29 The free‐energy profiles for the Ni‐catalyzed hydrocarboxylation...Figure 4.30 The free‐energy profiles for the Ni‐catalyzed hydrosilylation of...Figure 4.31 The free‐energy profiles for the Ni(II)‐catalyzed dihydrogenatio...Figure 4.32 The free‐energy profiles for the Ni‐catalyzed reductive carboxyl...Figure 4.33 The free‐energy profiles for the Ni‐catalyzed hydroamination of ...Scheme 4.12 Ni‐mediated cyclizations. (a) Annulations, (b) ring substitution...Scheme 4.13 The common mechanism of Ni‐catalyzed cycloadditions.Figure 4.34 The free‐energy profiles for the Ni‐catalyzed tetramerization of...Figure 4.35 The free‐energy profiles for the Ni‐catalyzed cycloaddition of d...Figure 4.36 The free‐energy profiles for the Ni(0)‐carbene catalyzed intramo...Figure 4.37 The free‐energy profiles for the Ni(0)‐carbene catalyzed cycload...Scheme 4.14 The mechanism of Ni‐mediated ring substitutions.Figure 4.38 The free‐energy profiles for the Ni‐catalyzed cycloaddition ring...Figure 4.39 The free‐energy profiles for the Ni‐catalyzed cycloaddition ring...Scheme 4.15 The mechanism of Ni‐mediated ring extensions.Figure 4.40 The free‐energy profiles for the Ni‐catalyzed ring extension of ...Figure 4.41 The free‐energy profiles for the Ni‐catalyzed ring extension of ...
5 Chapter 5Scheme 5.1 General mechanism of Pd‐catalyzed cross‐coupling reactions.Scheme 5.2 The mechanism of Suzuki–Miyaura cross‐coupling.Figure 5.1 The energy profiles for a model reaction of Pd‐catalyzed Suzuki–M...Scheme 5.3 (a) Pd‐catalyzed tandem Suzuki–Miyaura cross‐coupling with polyha...Scheme 5.4 Regioselectivity of Pa‐catalyzed Suzuki–Miyaura cross‐coupling wi...Figure 5.2 The free‐energy profiles for Pd‐catalyzed Suzuki–Miyaura cross‐co...Figure 5.3 The free‐energy profiles for Pd‐catalyzed Suzuki–Miyaura cross‐co...Figure 5.4 The calculated free energies for the key transition states of oxi...Scheme 5.5 Pd‐catalyzed Negishi coupling.Figure 5.5 The free‐energy profiles for a typical Pd‐catalyzed Negishi cross...Figure 5.6 The free‐energy profiles for a typical Pd‐catalyzed Negishi cross...Figure 5.7 The free‐energy profiles for the key step of transmetalation in P...Figure 5.8 The free‐energy profiles for the second transmetalation in Negish...Figure 5.9 The free‐energy profiles for a model reaction of Pd‐catalyzed Sti...Scheme 5.6 Pd‐catalyzed Hiyama coupling.Figure 5.10 The energy profiles for a model reaction of Pd‐catalyzed Hiyama ...Figure 5.11 The free‐energy profiles for a Pd‐catalyzed Hiyama coupling with...Scheme 5.7 Mechanism of Heck–Mizoroki reaction.Figure 5.12 The free‐energy profiles for a Pd‐catalyzed Heck–Mizoroki reacti...Figure 5.13 The free‐energy profiles for a Pd‐catalyzed Heck–Mizoroki reacti...Figure 5.14 The free‐energy profiles for a Pd‐catalyzed intramolecular Heck–...Scheme 5.8 Mechanism of Pd‐mediated C—hetero bond formations.Figure 5.15 The free‐energy profiles for the key steps of Pd‐catalyzed cross...Figure 5.16 The zero‐point energy profiles for a model reaction Pd‐catalyzed...Figure 5.17 The free‐energy profiles for a model reaction Pd‐catalyzed sulfu...Figure 5.18 The free‐energy profiles for intramolecular σ‐bond metathesis of...Figure 5.19 The free‐energy profiles for a Pd‐catalyzed C(alkyl)—I bond form...Figure 5.20 The free‐energy profiles for a Pd‐catalyzed conversion of aryl i...Scheme 5.9 Mechanism of Pd‐catalyzed silyation of unsaturated bonds.Figure 5.21 The energy profiles for a model reaction of Pd‐catalyzed bis‐sil...Figure 5.22 The free‐energy profiles for Pd‐catalyzed bis‐silylation of carb...Figure 5.23 The free‐energy profiles for Pd‐catalyzed intermolecular σ‐bond ...Scheme 5.10 Pd‐catalyzed C—H activation of methane.Figure 5.24 The free‐energy profiles for Pd‐catalyzed C—H activation of meth...Scheme 5.11 The transition states of Pd‐mediated C—H bond cleavage of proban...Scheme 5.12 Pd‐catalyzed C—H activation/arylation.Scheme 5.13 The calculated activation free energies for the Pd‐mediated C—H ...Scheme 5.14 Distortion–interaction analysis of the C—H bond cleavage step in...Figure 5.25 The free‐energy profiles for Pd‐catalyzed oxidative coupling of ...Figure 5.26 The free‐energy profiles for Pd‐catalyzed cross‐coupling of alde...Figure 5.27 The zero‐point energy profiles for the first‐reported Pd‐mediate...Scheme 5.15 The key transition states with (5‐231ts and 5‐232ts)...Scheme 5.16 Pd‐mediated covalent chelation‐assisted ortho‐ C(aryl)—H activat...Figure 5.28 The free‐energy profiles for Pd‐catalyzed oxidative coupling of ...Figure 5.29 The free‐energy profiles for the key step of Pd/Cu co‐catalyzed ...Scheme 5.17 The key transition states for the Pd‐mediated CMD‐type meta‐C—H ...Scheme 5.18 The key transition states for the Pd‐mediated CMD‐type meta‐C—H ...Scheme 5.19 The key transition states for the Pd‐mediated CMD‐type selective...Scheme 5.20 The key transition states for the Pd‐mediated CMD‐type covalent ...Figure 5.30 The free‐energy profiles of Pd‐catalyzed intramolecular cross‐co...Figure 5.31 The free‐energy profiles of Pd‐catalyzed β‐arylation of amides. ...Figure 5.32 The free‐energy profiles of norbornene‐assisted Pd‐catalyzed ind...Figure 5.33 The free‐energy profiles of the electrophilic deprotonation via ...Figure 5.34 The free‐energy profiles of Pd‐catalyzed azoles arylation reacti...Figure 5.35 The free‐energy profiles of Pd‐catalyzed intramolecular cross‐co...Figure 5.36 The free‐energy profiles of Pd‐catalyzed intramolecular carbene ...Figure 5.37 The free‐energy profiles of Pd‐catalyzed deformylation through a...Scheme 5.21 General mechanism of Pd‐catalyzed unsaturated bond activations: ...Figure 5.38 The free‐energy profiles for a model reaction of Pd‐catalyzed hy...Figure 5.39 The free‐energy profiles for a Pd‐catalyzed hydroarylation of ol...Figure 5.40 The energy profiles for a model reaction of Pd‐catalyzed hydroge...Figure 5.41 The free‐energy profiles for a model reaction of Pd‐catalyzed hy...Figure 5.42 The free‐energy profiles for Pd‐catalyzed Pauson–Khand reaction....Figure 5.43 The free‐energy profiles for Pd‐catalyzed hydroarylation of imin...Figure 5.44 The zero‐point energy profiles for Pd‐catalyzed alkoxycarbonylat...Figure 5.45 The zero‐point energy profiles for Pd‐catalyzed aminocarbonylati...Figure 5.46 The free‐energy profiles for Pd‐catalyzed tandem azide‐isocyanid...Figure 5.47 The free‐energy profiles for a model reaction of Pd‐catalyzed ca...Figure 5.48 The free‐energy profiles for a model reaction of a redox‐neutral...Figure 5.49 The free‐energy profiles for a model reaction of a redox‐involve...Scheme 5.22 The generation of allylic palladium. (a) Oxidative addition, (b)...Scheme 5.23 A typical mechanism of Pd‐mediated allylic substitution.Figure 5.50 The free‐energy profiles for Pd‐catalyzed Stille coupling with b...Figure 5.51 The free‐energy profiles for Pd‐catalyzed amination of allylic a...Figure 5.52 The free‐energy profiles for Pd‐catalyzed hydroamination of alle...Figure 5.53 The free‐energy profiles for Pd‐catalyzed isomerization of allyl...Figure 5.54 The free‐energy profiles for Pd‐catalyzed carbocyclization of bi...
6 Chapter 6Scheme 6.1 The possible mechanisms of Pt‐mediated C—H activations.Figure 6.1 Free‐energy profiles for the Pt‐catalyzed oxidation of methane in...Figure 6.2 Free‐energy profiles for the PtI4‐catalyzed intramolecular C—H an...Scheme 6.2 Possible mechanisms of Pt‐mediated C—H bond cleavage.Figure 6.3 Free‐energy profiles for the PtBr2‐catalyzed isomerization of eth...Figure 6.4 Free‐energy profiles for the PtCl2‐catalyzed cyclization of ortho Figure 6.5 Free‐energy profiles for the PtCl2‐catalyzed isomerization of 1,6...Figure 6.6 Free‐energy profiles for the PtCl2‐catalyzed cyclization of o‐alk...Figure 6.7 Free‐energy profiles for the PtCl2‐catalyzed isomerization of oxi...Figure 6.8 Free‐energy profiles for the PtCl2‐catalyzed cyclopropanation of ...Figure 6.9 Free‐energy profiles for the PtI2‐catalyzed cycloisomerization of...Scheme 6.3 Pt‐mediated annulation of enynes through a key step of oxidative ...Figure 6.10 Free‐energy profiles for the PtCl2‐catalyzed Alder‐ene type cycl...Scheme 6.4 The general mechanism of Pt‐mediated alkene functionalizations.Figure 6.11 Free‐energy profiles for the K2PtCl4‐NaBr‐catalyzed hydroaminati...Scheme 6.5 PtBr2‐catalyzed hydroamination of olefins.Figure 6.12 Free‐energy profiles for an amino‐Pt(II)‐catalyzed hydroaminatio...Figure 6.13 Free‐energy profiles for an amino‐Pt(II)‐catalyzed hydroformylat...Figure 6.14 Free‐energy profiles for an amino‐Pt(II)‐catalyzed isomerization...
7 Chapter 7Scheme 7.1 Possible models of cobalt‐mediated C—H activation.Scheme 7.2 (a) Co‐catalyzed C—H alkylations through olefin insertion and the...Figure 7.1 Free‐energy profiles for the low‐valent Co(0)‐catalyzed arene C—H...Figure 7.2 Free‐energy profiles for the high‐valent Co(III)‐catalyzed arene ...Figure 7.3 Free‐energy profiles for the Co(III)‐catalyzed hydroarylation of ...Figure 7.4 Free‐energy profiles for the Co(III)‐catalyzed hydroarylation of ...Figure 7.5 Free‐energy profiles for the Co(III)‐catalyzed hydroarylation of ...Figure 7.6 Free‐energy profiles for the Co(III)‐catalyzed oxidative alkoxyla...Scheme 7.3 General mechanism of Co‐catalyzed cycloadditions.Figure 7.7 Free‐energy profiles for a model Pauson–Khand reaction. The energ...Figure 7.8 Free‐energy profiles for a Co2(CO)8‐catalyzed intramolecular [4+2...Figure 7.9 Free‐energy profiles for a model reaction of CpCo(I)‐catalyzed [2...Figure 7.10 Free‐energy profiles for CpCo(I)‐mediated [2+2] cycloaddition of...Scheme 7.4 The general mechanism of Co‐catalyzed hydrogenation reactions.Figure 7.11 Free‐energy profiles for Co‐catalyzed hydrogenation of carbon di...Figure 7.12 Free‐energy profiles for Co‐catalyzed hydrogenation of carbon di...Figure 7.13 Free‐energy profiles for Co‐catalyzed hydrogenation of alkene th...Figure 7.14 Free‐energy profiles for Co‐catalyzed hydrogenation of alkene th...Figure 7.15 Free‐energy profiles for Co(−I)‐catalyzed hydrogenation of alken...Figure 7.16 Free‐energy profiles for Co‐catalyzed hydrogenation of alkyne. T...Scheme 7.5 Co‐catalyzed direct (a) and transfer (b) hydroformylations.Figure 7.17 Free‐energy profiles for a model reaction of Co‐catalyzed hydrof...Figure 7.18 Free‐energy profiles for a model reaction of Co‐catalyzed transf...Scheme 7.6 Mechanism of transition metal‐mediated diazo transformation.Figure 7.19 Free‐energy profiles for the Cp*Co(III)‐catalyzed annulation of ...Figure 7.20 Free‐energy profiles for the key step of Co‐mediated carboxylati...Scheme 7.7 The resonance structures of Co–nitrene complex (a); Calculated sp...Figure 7.21 Free‐energy profiles for the Co‐catalyzed aziridination of olefi...Figure 7.22 Free‐energy profiles for the Co‐catalyzed amination of isonitril...Figure 7.23 Relative enthalpy profiles for the Co‐mediated nitrene insertion...
8 Chapter 8Scheme 8.1 General mechanism of Rh‐catalyzed C—H activation and functionaliz...Figure 8.1 Free‐energy profiles for Rh(I)‐catalyzed C2‐selective C—H bond ac...Figure 8.2 Free‐energy profiles for Rh(III)‐catalyzed oxidative C—H/C—H cros...Figure 8.3 Free‐energy profiles for Rh(III)‐catalyzed bipyridine C—H alkylat...Figure 8.4 Free‐energy profiles for the key step of Rh/7‐azaindoline co‐cata...Figure 8.5 Free‐energy profiles for Cp*Rh(III)‐catalyzed C—H bond alkylation...Figure 8.6 Free‐energy profiles for Rh(III)‐catalyzed oxidative Heck‐type co...Figure 8.7 Free‐energy profiles for Rh(III)‐catalyzed alkenylation of 8‐meth...Figure 8.8 Free‐energy profiles for Rh(III)‐catalyzed intermolecular C—H bon...Figure 8.9 Free‐energy profiles for Rh(III)‐catalyzed ortho‐C—H bond activat...Scheme 8.2 The general pathways for the Rh mediated C—C bond cleavage.Figure 8.10 Free‐energy profiles for Rh‐catalyzed intramolecular ring expans...Figure 8.11 Free‐energy profiles for Rh‐catalyzed borylation of nitriles. Th...Figure 8.12 Free‐energy profiles for Rh‐catalyzed ring‐opening reactions of ...Figure 8.13 Free‐energy profiles for Rh‐catalyzed ring‐expansion of aziridin...Figure 8.14 Free‐energy profiles for Rh‐catalyzed pyridinyl‐assisted C—O bon...Scheme 8.3 General mechanism of Rh‐catalyzed alkene functionalizations.Figure 8.15 Free‐energy profiles for Rh‐catalyzed hydrogenation of alkene. T...Figure 8.16 Free‐energy profiles for Rh‐catalyzed hydrogenation of alkene. T...Figure 8.17 Free‐energy profiles for Rh‐catalyzed diboration of alkene. The ...Figure 8.18 Free‐energy profiles for Rh‐catalyzed intramolecular hydrocylati...Figure 8.19 Free‐energy profiles for Rh‐catalyzed hydroamination of alkynes....Figure 8.20 Energy profiles for Rh‐catalyzed hydrothiolation of alkynes. The...Figure 8.21 Energy profiles for Rh‐catalyzed hydroacetoxylation of alkynes. ...Figure 8.22 Free‐energy profiles for Rh‐catalyzed hydrogenation of ketones. ...Figure 8.23 Free‐energy profiles for Rh‐mediated hydrogenation of carbon dio...Figure 8.24 Free‐energy profiles for Rh‐catalyzed hydroacylation of ketones....Scheme 8.4 General mechanism of Rh‐mediated carbene transformations. (a) Con...Figure 8.25 Free‐energy profiles for dirhodium‐catalyzed carbene insertion i...Figure 8.26 Free‐energy profiles for dirhodium‐catalyzed carbene insertion i...Figure 8.27 Energy profiles for dirhodium‐catalyzed cyclopropanation of carb...Figure 8.28 Free‐energy profiles for dirhodium‐catalyzed cyclopropenation of...Figure 8.29 Free‐energy profiles for rhodium‐mediated nitrene insertion into...Figure 8.30 Free‐energy profiles for rhodium‐catalyzed nitrene insertion int...Figure 8.31 Free‐energy profiles for rhodium‐catalyzed intramolecular azirid...Scheme 8.5 General mechanism of Rh‐catalyzed cycloadditions.Figure 8.32 Free‐energy profiles for rhodium‐catalyzed intramolecular (3+2) ...Figure 8.33 Free‐energy profiles for rhodium‐catalyzed formal (3+2) cycloadd...Figure 8.34 Free‐energy profiles for rhodium‐catalyzed Pauson–Khand reaction...Figure 8.35 Free‐energy profiles for rhodium‐catalyzed intermolecular (5+2) ...Figure 8.36 Free‐energy profiles for rhodium‐catalyzed intermolecular (5+2) ...Figure 8.37 Free‐energy profiles for rhodium‐catalyzed (5+2+1) cycloaddition...
9 Chapter 9Scheme 9.1 Ir‐catalyzed hydrogenations. (a) Direct hydrogenation. (b) Transf...Scheme 9.2 Mechanism of Ir‐catalyzed hydrogenation of alkenes.Figure 9.1 The free‐energy profiles for the Ir‐catalyzed hydrogenation of al...Figure 9.2 The free‐energy profiles for the Ir‐catalyzed hydrogenation of al...Scheme 9.3 General mechanism of Ir‐catalyzed hydrogenation of a carbonyl com...Figure 9.3 The free‐energy profiles for the Ir‐catalyzed hydrogenation of ke...Figure 9.4 The free‐energy profiles for the Ir‐catalyzed hydrogenation of es...Scheme 9.4 General mechanism of Ir‐catalyzed hydrogenation of imines.Figure 9.5 The free‐energy profiles for the Ir‐catalyzed hydrogenation of im...Figure 9.6 The free‐energy profiles for the Ir‐catalyzed hydrogenation of qu...Figure 9.7 The free‐energy profiles for the Ir‐catalyzed intramolecular hydr...Scheme 9.5 General mechanism of Ir‐catalyzed hydroarylation of unsaturated b...Figure 9.8 The free‐energy profiles for the Ir‐catalyzed hydroarylation of a...Figure 9.9 The free‐energy profiles for the Ir‐catalyzed hydrosilylation of ...Figure 9.10 The free‐energy profiles for the Ir‐catalyzed hydrosilylation of...Figure 9.11 The free‐energy profiles for the Ir(III)‐catalyzed hydrosilylati...Figure 9.12 The free‐energy profiles for the Ir‐catalyzed borylation of alka...Figure 9.13 The free‐energy profiles for the Ir‐catalyzed borylation of aren...Figure 9.14 The free‐energy profiles for the Ir‐catalyzed borylation of aren...Scheme 9.6 Mechanism of Ir‐catalyzed amination of alcohols.Figure 9.15 The free‐energy profiles for the Ir‐catalyzed amination of alcoh...Figure 9.16 The free‐energy profiles for the Ir‐catalyzed amination of arene...Figure 9.17 The free‐energy profiles for the Ir‐catalyzed arylation of alkan...Figure 9.18 The free‐energy profiles for the Ir‐catalyzed arylation of arene...
10 Chapter 10Scheme 10.1 The generation of iron‐oxo species.Figure 10.1 Energy profiles for the iron‐catalyzed C(alkyl)—H oxidation. The...Figure 10.2 Energy profiles for the iron‐oxo mediated methane oxidation. The...Scheme 10.2 Possible reaction modes for the arene oxidation by iron‐oxo comp...Figure 10.3 (a) A comparative study of the iron‐oxo oxidation of benzene. (b...Figure 10.4 Free‐energy profiles for the iron‐mediated oxidative ortho‐hydro...Figure 10.5 Free‐energy profiles for the iron‐mediated oxidation of alkenes ...Figure 10.6 Energy profiles for the iron‐catalyzed oxidative extradiol oxida...Figure 10.7 Energy profiles for the iron‐catalyzed hydrogenation of alkenes....Figure 10.8 Free‐energy profiles for the ligand‐assisted iron‐catalyzed hydr...Figure 10.9 Free‐energy profiles for the iron‐catalyzed hydrogenation of ket...Figure 10.10 Free‐energy profiles for the iron‐catalyzed hydrogenation of im...Figure 10.11 Relative enthalpy profiles for the iron‐catalyzed hydrogenation...Figure 10.12 Free‐energy profiles for the outer‐sphere catalytic cycle of ir...Figure 10.13 Free‐energy profiles for the inner‐sphere catalytic cycle of th...Figure 10.14 Free‐energy profiles for the iron‐catalyzed intramolecular hydr...Scheme 10.3 Dehydrogenation of alcohols.Figure 10.15 Free‐energy profiles for the iron‐catalyzed dehydrogenation of ...Figure 10.16 Free‐energy profiles for the iron‐catalyzed dehydrogenation of ...Figure 10.17 Free‐energy profiles for the iron‐catalyzed dehydrogenation of ...Figure 10.18 Free‐energy profiles for the iron‐catalyzed dehydrogenation of ...Figure 10.19 Free‐energy profiles for the iron‐catalyzed Kumada‐type couplin...Figure 10.20 Free‐energy profiles for the iron‐catalyzed amination of aryl b...Figure 10.21 Free‐energy profiles for the iron‐catalyzed arylation of alkyl ...Figure 10.22 Free‐energy profiles for the iron‐catalyzed oxidative coupling ...
11 Chapter 11Scheme 11.1 A model reaction of Ru‐mediated CMD‐type C—H activation. The ene...Scheme 11.2 Phosphite Ru(II)‐mediated C—H activation of arenes. The energies...Scheme 11.3 Ru‐mediated C—H bond activation of benzamide via BIES‐type trans...Scheme 11.4 Ru‐mediated C—H arylation with aryl bromide through σ‐CAM‐type C...Scheme 11.5 Comparison of CMD‐ and σ‐CAM‐type C—H activations in Ru‐mediated...Scheme 11.6 Ru‐mediated C—H bond activation/vinylation through oxidative add...Scheme 11.7 Ru‐mediated C—H bond activation/alkanation through oxidative add...Scheme 11.8 Ru‐catalyzed C—H bond functionalization with electrophiles or nu...Scheme 11.9 General mechanism of Ru‐catalyzed C—H bond arylation with an ele...Figure 11.1 Free‐energy profiles of the Ru‐catalyzed C—H bond arylation. The...Scheme 11.10 General mechanism of Ru‐catalyzed C—H bond activation with nucl...Figure 11.2 Free‐energy profiles of Ru‐catalyzed C—H bond functionalization ...Scheme 11.11 General mechanism of Ru‐catalyzed alkylation of arenes with ole...Figure 11.3 Free‐energy profiles of Ru‐catalyzed decarboxylative ortho‐alkyl...Figure 11.4 Free‐energy profiles of Ru‐catalyzed oxidative ortho‐alkenylatio...Figure 11.5 Free‐energy profiles of Ru‐catalyzed oxidative ortho‐alkenylatio...Figure 11.6 Potential energy profiles of Ru‐catalyzed pyridine C—H alkenylat...Figure 11.7 Free‐energy profiles of Ru‐catalyzed hydrogenation of alkenes. T...Figure 11.8 Potential energy profiles of Ru‐catalyzed hydrogenation of keton...Figure 11.9 Free‐energy profiles of Ru‐catalyzed hydrogenation of esters. Th...Figure 11.10 Free‐energy profiles of Ru‐catalyzed hydrodefluorination of flu...Scheme 11.12 General mechanism of Ru‐hydride catalyzed hydroacylation of ole...Figure 11.11 Free‐energy profiles of Ru‐catalyzed hydrodefluorination of flu...Scheme 11.13 Ru‐catalyzed hydrocarboxylation of terminal alkynes.Figure 11.12 Free‐energy profiles of Ru‐catalyzed hydrocarboxylations of phe...Figure 11.13 Free‐energy profiles of Ru‐catalyzed hydrocarboxylations of phe...Figure 11.14 Free‐energy profiles of Ru‐catalyzed trans‐hydroboration of ace...Scheme 11.14 Dehydrogenation of methanol in the presence of pincer‐PNP coord...Figure 11.15 Free‐energy profiles of methanol‐assisted hydrogen desorption i...Figure 11.16 Free‐energy profiles for the Ru‐mediated dehydrogenation of met...Figure 11.17 Free‐energy profiles for the Ru‐mediated dehydrogenation of for...Figure 11.18 Free‐energy profiles for the Ru‐mediated dehydrogenation of for...Scheme 11.15 The oxidative cycloaddition of diyne onto Ru.Figure 11.19 Free‐energy profiles for the Ru‐catalyzed cyclotrimerization of...Figure 11.20 Free‐energy profiles for the Ru‐catalyzed intramolecular Pauson...Figure 11.21 Free‐energy profiles for the Ru‐catalyzed click reaction throug...Figure 11.22 Free‐energy profiles for the Ru‐catalyzed click reaction throug...Scheme 11.16 Ru‐mediated olefin metathesis.Figure 11.23 Free‐energy profiles for the generation of active catalyst in a...Figure 11.24 Free‐energy profiles for the catalytic cycle of Grubbs II–type ...Figure 11.25 Free‐energy profiles for the catalytic cycle of Ru‐catalyzed in...Figure 11.26 Free‐energy profiles for the catalytic cycle of Ru‐catalyzed in...
12 Chapter 12Scheme 12.1 General mechanism for Mn‐mediated alkane oxidation.Scheme 12.2 Porphyrin‐coordinated Mn(V) species. Corresponding spin densitie...Figure 12.1 Potential energy profiles for the C(alkyl)‐H oxidation by using ...Scheme 12.3 Manganese porphyrin–catalyzed C(alkyl)‐H fluorination with fluor...Scheme 12.4 Manganese porphyrin–catalyzed C(alkyl)‐H azidation with azide. T...Figure 12.2 Free‐energy profiles for the Mn‐catalyzed C(alkyl)‐H isocyanatio...Scheme 12.5 General modes of Mn‐mediated C—H activations.Figure 12.3 Potential energy profiles for the Mn‐catalyzed C(aryl)‐H alkylat...Figure 12.4 Free‐energy profiles for the Mn‐catalyzed C(aryl)‐H alkylation t...Figure 12.5 Free‐energy profiles for the Mn‐catalyzed dehydrogenative annula...Figure 12.6 Free‐energy profiles for the Mn‐catalyzed annulation of aryl imi...Figure 12.7 Free‐energy profiles for the Mn‐catalyzed hydrogenation of carbo...Figure 12.8 Free‐energy profiles for the Mn‐catalyzed hydrogenation of carbo...Figure 12.9 Free‐energy profiles for the Mn‐catalyzed dehydrogenation of met...Figure 12.10 Free‐energy profiles for the Mn‐catalyzed dehydrogenative coupl...
13 Chapter 13Scheme 13.1 (a) Ullmann reactions and (b) Ullmann condensations.Scheme 13.2 General mechanism of Ullmann condensations: (a) oxidative additi...Figure 13.1 Free‐energy profiles for the Cu‐catalyzed Ullmann condensation o...Figure 13.2 Free‐energy profiles for the Cu‐catalyzed Ullmann condensation o...Figure 13.3 Free‐energy profiles for the Cu‐catalyzed Ullmann condensation t...Figure 13.4 Free‐energy profiles for the Cu‐catalyzed Ullmann condensation t...Figure 13.5 Free‐energy profiles for the trifluoromethylation of iodobenzene...Figure 13.6 Free‐energy profiles for the Cu‐catalyzed trifluoromethylation o...Scheme 13.3 The generation of CF3 radical.Figure 13.7 Free‐energy profiles for the Cu‐catalyzed trifluoromethylation o...Figure 13.8 Free‐energy profiles of copper‐catalyzed oxytrifluoromethylation...Figure 13.9 Free‐energy profiles of copper‐catalyzed arylation of heterocycl...Figure 13.10 Free‐energy profiles of copper‐catalyzed meta‐arylation of C(ar...Figure 13.11 Free‐energy profiles of copper‐catalyzed intramolecular C(aryl)...Figure 13.12 Free‐energy profiles of copper‐catalyzed oxidative hydroxylatio...Figure 13.13 Free‐energy profiles of copper‐catalyzed C‐H etherifications of...Scheme 13.4 Cu‐mediated alkyne activation modes. (a) Alkyne insertion, (b) o...Scheme 13.5 Cu‐catalyzed [3+2] cycloadditions of terminal alkynes and organi...Figure 13.14 Potential energy profiles of Cu‐catalyzed [3+2] cycloadditions ...Figure 13.15 Free‐energy profiles of Cu‐catalyzed [3+2] cycloadditions of te...Figure 13.16 Free‐energy profiles of Cu‐catalyzed [3+2] cycloadditions of te...Figure 13.17 Free‐energy profiles of the competition of intramolecular 5‐exo...Figure 13.18 Free‐energy profiles of the competition of intramolecular exo‐h...Figure 13.19 Free‐energy profiles for the copper‐catalyzed cross‐coupling of...Figure 13.20 Free‐energy profiles of Cu(II)‐mediated oxidative homo‐coupling...Scheme 13.6 Possible mechanism of Cu‐mediated [2+1] cycloadditions of carben...Figure 13.21 Free‐energy profiles of Cu‐catalyzed [2+1] cycloadditions of ca...Figure 13.22 Free‐energy profiles of Cu‐catalyzed carbene insertion into C(a...Figure 13.23 Free‐energy profiles of Cu‐mediated transformation from α‐diazo...Figure 13.24 Free‐energy profiles of Cu‐catalyzed [2+1] cycloadditions of ni...Figure 13.25 Free‐energy profiles of Cu‐mediated intramolecular amination of...Figure 13.26 Free‐energy profiles of Cu‐catalyzed nitrene insertion into C(a...Scheme 13.7 General mechanism of cuprous‐hydride‐catalyzed hydrofunctionaliz...Figure 13.27 Free‐energy profiles of Cu‐catalyzed hydroborylation of alkynes...Figure 13.28 Free‐energy profiles of Cu‐catalyzed hydrosilylation of ketones...Figure 13.29 Free‐energy profiles of Cu‐catalyzed hydrocarboxylation of alky...Scheme 13.8 General mechanism of cuprous‐catalyzed borylations.Figure 13.30 Free‐energy profiles of Cu‐catalyzed alkylborylation of alkenes...Figure 13.31 Free‐energy profiles of Cu‐catalyzed hydroborylation of alkenes...Figure 13.32 Free‐energy profiles of Cu‐catalyzed boracatboxylation of styre...Figure 13.33 Free‐energy profiles of Cu‐catalyzed hydroborylation of enterna...Figure 13.34 Free‐energy profiles of Cu‐catalyzed diborylation of aldehydes....Figure 13.35 Free‐energy profiles of Cu‐catalyzed reduction of carbon dioxid...
14 Chapter 14Scheme 14.1 (a) Electron configuration of singlet and triplet carbene; (b) m...Scheme 14.2 General mechanism of silver‐catalyzed carbene transfer reactions...Scheme 14.3 Two activation models of a diazo compound with an Ag species: (a...Figure 14.1 Free‐energy profiles of possible pathways for carbene formation ...Figure 14.2 Free‐energy profiles of carbene formation in Ag‐catalyzed carben...Figure 14.3 Potential energy profiles of Ag‐catalyzed carbene insertion into...Scheme 14.4 Regioselectivity of the nucleophilic addition of a hydroxyl grou...Figure 14.4 Free‐energy profiles for the nucleophilic addition of the carbon...Figure 14.5 Free‐energy profiles of Ag‐catalyzed carbene insertion into the ...Figure 14.6 Free‐energy profiles of possible pathways for carbene insertion ...Scheme 14.5 (a) A triplet nitrene. (b) Triplet Ag(I)–nitrene complex with tw...Figure 14.7 Free‐energy profiles for the formation of a triplet Ag–nitrene c...Figure 14.8 Free‐energy profiles for Ag–nitrene complex formation in N‐amida...Scheme 14.6 Two possible pathways for transition metal‐supported olefin azir...Figure 14.9 Free‐energy profiles for the Ag‐mediated aziridination of alkene...Figure 14.10 Free‐energy profiles for the nucleophilic addition of an amine ...Scheme 14.7 Mechanism of Ag‐catalyzed silylene transfer reactions.Figure 14.11 Free‐energy profiles for the Ag‐catalyzed silylene transfer rea...Scheme 14.8 Ag‐meditated alkyne activation modes: (a) π‐activation and (b) C...Figure 14.12 Free‐energy profiles for the Ag‐catalyzed annulation of proparg...Figure 14.13 Free‐energy profiles for the Ag‐catalyzed decomposition of prop...Figure 14.14 Free‐energy profiles for the Ag‐catalyzed carboxylation of term...
15 Chapter 15Scheme 15.1 General mechanism of gold‐catalyzed unsaturated bond functionali...Scheme 15.2 Trans‐nucleophilic attack of gold–alkyne complex.Figure 15.1 The free‐energy profiles for the gold‐catalyzed isomerization of...Figure 15.2 The free‐energy profiles for the gold‐catalyzed hydroalkoxylatio...Figure 15.3 The free‐energy profiles for the gold‐catalyzed 4+2 annulation o...Figure 15.4 The free‐energy profiles for the gold‐catalyzed rearrangements o...Figure 15.5 The free‐energy profiles for the gold‐catalyzed oxyarylation of ...Figure 15.6 The free‐energy profiles for the gold‐catalyzed intermolecular h...Figure 15.7 The free‐energy profiles for the gold‐catalyzed cyclization of a...Figure 15.8 The free‐energy profiles for the gold‐catalyzed isomerization of...Figure 15.9 The free‐energy profiles for the gold‐catalyzed intramolecular h...Figure 15.10 The free‐energy profiles for the gold‐catalyzed intermolecular ...Figure 15.11 The free‐energy profiles for the gold‐catalyzed intermolecular ...Scheme 15.3 General mechanism of gold‐catalyzed allylic substitutions.Figure 15.12 The free‐energy profiles for the gold‐catalyzed sigmatropic rea...Figure 15.13 The free‐energy profiles for the gold‐catalyzed etherification ...Figure 15.14 The free‐energy profiles for the gold‐catalyzed hydroamination ...Figure 15.15 The potential energy profiles for the gold‐catalyzed hydroalkox...Figure 15.16 The free‐energy profiles for the gold‐catalyzed cycloisomerizat...Figure 15.17 The free‐energy profiles for the gold‐catalyzed cycloisomerizat...Figure 15.18 The free‐energy profiles for the gold‐catalyzed cycloisomerizat...Figure 15.19 The free‐energy profiles for the gold‐catalyzed cycloisomerizat...Figure 15.20 The free‐energy profiles for the gold‐catalyzed cycloisomerizat...Figure 15.21 The free‐energy profiles for the gold‐catalyzed cycloisomerizat...Figure 15.22 The free‐energy profiles for the gold‐catalyzed cycloisomerizat...
