Yu Lan - Computational Methods in Organometallic Catalysis

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...