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Computational Methods in Organometallic Catalysis
Discover recent advances in the mechanistic study of organometallic catalysis
In Computational Methods in Organometallic Catalysis: From Elementary Reactions to Mechanisms, distinguished chemist and author Yu Lan delivers a synthesis of the use of calculation methods and experimental techniques to improve the efficiency of reaction and yield of product and to uncover the factors that control the selectivity of product. Providing not only a theoretical overview of organometallic catalysis, the book also describes computational studies for the mechanism of transition-metal-assisted reactions.
You’ll learn about Ni-, Pd-, Pt-, Co-, Rh-, Ir-, Fe-, Ru-, Mn-, Cu-, Ag-, and Au- catalysis. You’ll also discover many of the experimental and theoretical advances in organometallic catalysis reported in the recent literature. The book summarizes and generalizes the advances made in the mechanistic study of organometallic catalysis.
Readers will also benefit from the inclusion of:
- A thorough introduction to computational organometallic chemistry, including a brief history of the discipline and the use of computational tools to study the mechanism of organometallic chemistry
- An exploration of computational methods in organometallic chemistry, including density functional theory methods and basis sets and their application in mechanism studies
- A practical discussion of elementary reactions in organometallic chemistry, including coordination and dissociation, oxidative addition, reductive elimination, insertion, elimination, transmetallation, and metathesis
- A concise treatment of the theoretical study of transition-metal catalysis.
Perfect for organic, catalytic, complex, and structural chemists, Computational Methods in Organometallic Catalysis will also earn a place in the libraries of theoretical chemists seeking a one-stop organometallic catalysis resource with a focus on the mechanism of transition-metal-assisted reactions.
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Seitenzahl: 971
Veröffentlichungsjahr: 2021
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Table of Contents
Cover
Title Page
Copyright
Foreword
Preface
Part I: Theoretical View of Organometallic Catalysis
1 Introduction of Computational Organometallic Chemistry
1.1 Overview of Organometallic Chemistry
1.2 Using Computational Tool to Study the Organometallic Chemistry Mechanism
References
2 Computational Methods in Organometallic Chemistry
2.1 Introduction of Computational Methods
2.2 Density Functional Theory (DFT) Methods
2.3 Basis Set and Its Application in Mechanism Studies
2.4 Solvent Effect
2.5 How to Choose a Method in Computational Organometallic Chemistry
2.6 Revealing a Mechanism for An Organometallic Reaction by Theoretical Calculations
2.7 Overview of Popular Computational Programs
2.8 The Limitation of Current Computational Methods
References
3 Elementary Reactions in Organometallic Chemistry
3.1 General View of Elementary Reactions in Organometallic Chemistry
3.2 Coordination and Dissociation
3.3 Oxidative Addition
3.4 Reductive Elimination
3.5 Insertion
3.6 Elimination
3.7 Transmetallation
3.8 Metathesis
References
Part II: On the Mechanism of Transition‐metal‐assisted Reactions
4 Theoretical Study of Ni‐Catalysis
4.1 Ni‐Mediated C—H Bond Activation
4.2 Ni‐Mediated C—Halogen Bond Cleavage
4.3 Ni‐Mediated C—O Bond Activation
4.4 Ni‐Mediated C—N Bond Cleavage
4.5 Ni‐Mediated C—C Bond Cleavage
4.6 Ni‐Mediated Unsaturated Bond Activation
4.7 Ni‐Mediated Cyclization
References
5 Theoretical Study of Pd‐Catalysis
5.1 Pd‐Catalyzed Cross‐coupling Reactions
5.2 Pd‐Mediated C—Hetero Bond Formation
5.3 Pd‐Mediated C—H Activation Reactions
5.4 Pd‐Mediated Activation of Unsaturated Molecules
5.5 Allylic Pd Complex
References
6 Theoretical Study of Pt‐Catalysis
6.1 Mechanism of Pt‐Catalyzed C—H Activation
6.2 Mechanism of Pt‐Catalyzed Alkyne Activation
6.3 Mechanism of Pt‐Catalyzed Alkene Activation
References
7 Theoretical Study of Co‐Catalysis
7.1 Co‐Mediated C—H Bond Activation
7.2 Co‐Mediated Cycloadditions
7.3 Co‐Catalyzed Hydrogenation
7.4 Co‐Catalyzed Hydroformylation
7.5 Co‐Mediated Carbene Activation
7.6 Co‐Mediated Nitrene Activation
References
8 Theoretical Study of Rh‐Catalysis
8.1 Rh‐Mediated C—H Activation Reactions
8.2 Rh‐Catalyzed C—C Bond Activations and Transformations
8.3 Rh‐Mediated C—Hetero Bond Activations
8.4 Rh‐Catalyzed Alkene Functionalizations
8.5 Rh‐Catalyzed Alkyne Functionalizations
8.6 Rh‐Catalyzed Addition Reactions of Carbonyl Compounds
8.7 Rh‐Catalyzed Carbene Transformations
8.8 Rh‐Catalyzed Nitrene Transformations
8.9 Rh‐Catalyzed Cycloadditions
References
9 Theoretical Study of Ir‐Catalysis
9.1 Ir‐Catalyzed Hydrogenations
9.2 Ir‐Catalyzed Hydrofunctionalizations
9.3 Ir‐Catalyzed Borylations
9.4 Ir‐Catalyzed Aminations
9.5 Ir‐Catalyzed C—C Bond Coupling Reactions
References
10 Theoretical Study of Fe‐Catalysis
10.1 Fe‐Mediated Oxidations
10.2 Fe‐Mediated Hydrogenations
10.3 Fe‐Mediated Hydrofunctionalizations
10.4 Fe‐Mediated Dehydrogenations
10.5 Fe‐Catalyzed Coupling Reactions
References
11 Theoretical Study of Ru‐Catalysis
11.1 Ru‐Mediated C—H Bond Activation
11.2 Ru‐Catalyzed Hydrogenations
11.3 Ru‐Catalyzed Hydrofunctionalizations
11.4 Ru‐Mediated Dehydrogenations
11.5 Ru‐Catalyzed Cycloadditions
11.6 Ru‐Mediated Metathesis
References
12 Theoretical Study of Mn‐Catalysis
12.1 Mn‐Mediated Oxidation of Alkanes
12.2 Mn‐Mediated C—H Activations
12.3 Mn‐Mediated Hydrogenations
12.4 Mn‐Mediated Dehydrogenations
References
13 Theoretical Study of Cu‐Catalysis
13.1 Cu‐Mediated Ullmann Condensations
13.2 Cu‐Mediated Trifluoromethylations
13.3 Cu‐Mediated C—H Activations
13.4 Cu‐Mediated Alkyne Activations
13.5 Cu‐Mediated Carbene Transformations
13.6 Cu‐Mediated Nitrene Transformations
13.7 Cu‐Catalyzed Hydrofunctionalizations
13.8 Cu‐Catalyzed Borylations
References
14 Theoretical Study of Ag‐Catalysis
14.1 Ag‐Mediated Carbene Complex Transformations
14.2 Ag‐Mediated Nitrene Transformations
14.3 Ag‐Mediated Silylene Transformations
14.4 Ag‐Mediated Alkyne Activations
References
15 Theoretical Study of Au‐Catalysis
15.1 Au‐Mediated Alkyne Activations
15.2 Au‐mediated Alkene Activations
15.3 Au‐mediated Allene Activations
15.4 Au‐mediated Enyne Transformations
References
Index
End User License Agreement
List of Tables
Chapter 2
Table 2.1 Properties of frequently used approaches for the dispersion correct...
Table 2.2 Scaling behaviors of computational methods.
List of Illustrations
Chapter 1
Scheme 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(CH
2
NBn
2
)
+
.
Scheme 1.6 Mechanism of rhodium‐catalyzed coupling reaction of quinoline
N
‐o...
Scheme 1.7 Mechanism study of organometallic catalysis by density functional...
Chapter 2
Scheme 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...
Chapter 3
Scheme 3.1 The coordination of ligand onto metal.
Scheme 3.2 Back‐donation bonds in metal‐η
2
–alkene (a), metal‐η
2
–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 Cl
2
P...
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 S
N
2‐substitution‐type oxidative...
Figure 3.13 The free‐energy profiles for the S
N
2‐substitution‐type oxidative...
Figure 3.14 The free‐energy profiles for the S
N
Ar‐ 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)(NMe
Figure 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. ...
Chapter 4
Scheme 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 ...
Chapter 5
Scheme 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...
Chapter 6
Scheme 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 PtI
4
‐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 PtBr
2
‐catalyzed isomerization of eth...
Figure 6.4 Free‐energy profiles for the PtCl
2
‐catalyzed cyclization of
ortho
Figure 6.5 Free‐energy profiles for the PtCl
2
‐catalyzed isomerization of 1,6...
Figure 6.6 Free‐energy profiles for the PtCl
2
‐catalyzed cyclization of
o
‐alk...
Figure 6.7 Free‐energy profiles for the PtCl
2
‐catalyzed isomerization of oxi...
Figure 6.8 Free‐energy profiles for the PtCl
2
‐catalyzed cyclopropanation of ...
Figure 6.9 Free‐energy profiles for the PtI
2
‐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 PtCl
2
‐catalyzed Alder‐ene type cycl...
Scheme 6.4 The general mechanism of Pt‐mediated alkene functionalizations.
Figure 6.11 Free‐energy profiles for the K
2
PtCl
4
‐NaBr‐catalyzed hydroaminati...
Scheme 6.5 PtBr
2
‐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...
Chapter 7
Scheme 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 Co
2
(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...
Chapter 8
Scheme 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...
Chapter 9
Scheme 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...
Chapter 10
Scheme 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 ...
Chapter 11
Scheme 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...
Chapter 12
Scheme 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...
Chapter 13
Scheme 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 CF
3
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...
Chapter 14
Scheme 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...
Chapter 15
Scheme 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...
Guide
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Computational Methods in Organometallic Catalysis
From Elementary Reactions to Mechanisms
Yu Lan
Author
Prof. Yu Lan
Zhengzhou UniversityGreen Catalysis Center, and College of Chemistry450001 ZhengzhouChina
Cover Image: ©Vikks/Shutterstock
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Print ISBN: 978‐3‐527‐34601‐1ePDF ISBN: 978‐3‐527‐34605‐9ePub ISBN: 978‐3‐527‐34603‐5oBook ISBN: 978‐3‐527‐34602‐8
Foreword
Computational chemistry began in the 1940s with the earliest electronic computers and drastic approximations to the Schrödinger equation, such as Hückel molecular orbital theory. Since the 1960s, the possibilities of doing quantum mechanics calculations on large systems containing metals, indeed to study the heart of organometallic chemistry, began with the Mulliken–Wolfsberg–Helmholtz approach and then Roald Hoffmann's Extended Hückel Theory (EHT) in the 1950s and 1960s. While an amazingly useful method, EHT is really only of qualitative value. But actually what we need is a conceptual framework that is useful even today.
The 1960s saw remarkable advances in methods, approximations, and the beginnings of the flowering of computers for chemical calculations. The dawn of the modern hybrid density functional theory in the mid‐1990s, borrowing exact exchange from wavefunction theory, made it possible to begin the quantitative calculations of structure, mechanics, and mechanisms, including the incredibly useful organometallic reactions. Both Ru and Mo catalysts for olefin metathesis, and Pd catalysis for cross‐coupling reactions, have led to Nobel prizes for their discoverers.
Yu Lan has now written an introduction, a guide, a masterwork about quantum mechanical studies of organometallic reaction mechanisms. He is ideally equipped to write such a book, already doing outstanding work in the field as a student and postdoc, and becoming a leader in the field in his independent career. He has also trained many young experts in the field, and his influence will spread further from their achievements and through this book.
The book includes a historical introduction to organometallic chemistry, a survey of mechanisms, and an extensive introduction to quantum mechanical computational methods, especially density functional theory, as well as programs for quantum chemical calculations.
The description of organometallic structures and mechanisms is peppered with numerous calculations from the Lan group with relatively accurate density functionals. Part 2, the bulk of this book, is organized with a chapter for each of the most important metals used in organometallic chemistry: Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Mn, Cu, Ag, and Au. The computational studies of the reactions of complexes of each of these metals are reviewed with great insights into mechanisms using computations.
The book will be a boon to organometallic chemists and computational chemists involved in the study of organometallic reactions. While a number of books on organometallic chemistry mechanisms are available, this is THE book describing the methods for computation and analysis of organometallic reactions using modern quantum mechanical methods.
29 August 2020
Kendall N. Houk
Preface
A long time ago, when I first came into contact with science, I was fascinated by the unique charm of organic chemistry. The tetravalent carbon atoms and their tetrahedral structures impressed me with elegant simplicity. Through the broken and formation of covalent bonds, various new molecules that possess unique properties could be generated. By manipulating the reaction conditions, catalysts, and ligands in organic reactions, chemists can effectively synthesize plenty of complex natural product molecules and pharmaceutical molecules in high regioselectivity and enantioselectivity. When I was a teenager, I took every organic chemical reaction as a puzzle, and the reaction mechanism is like the answer to the puzzle. In this way, I found great pleasure in thinking about the mechanism of organic reactions. The development of organic chemistry also requires a comprehensive mechanistic understanding. Generally, a significant amount of information about reaction mechanisms could be obtained by experimental techniques. However, the experimental mechanistic study mainly focuses on the macroscopically observed experimental phenomena. Therefore, in many cases, pure experimental observation is not sufficient for revealing the complete reaction pathway and clarifying the origin of selectivity. During my doctoral study at Peking University, I was fortunate to work with my supervisor Professor Yun‐Dong Wu, from whom I learned how to use computational chemistry to investigate the organic reaction mechanisms. Theoretical calculations based on quantum mechanics, especially the density functional theory calculation, have constituted the most powerful tool for mechanistic study due to the development of supercomputer, computational theory, and corresponding software.
In the past several decades, one of the most important advances in organic chemistry has been the introduction of transition metal catalysts to organic synthesis. Transition metal species can react with organic compounds to generate intermediates that contain carbon–metal bonds. Subsequent conversion of these organometallic intermediates could enrich the synthetic approach toward new molecules. Different from organocatalysis, the organometallic catalysis usually goes through multiple steps and complicated catalytic cycles, which originated from the complex bonding pattern of organometallic catalysts and the variation of valance state of the central metal species. Thus, the utilization of theoretical calculation for understanding the reaction mechanism is imperative for the development of organic chemistry. My post‐doctoral research with Professor K. N. Houk was working with experimental chemists to explore the mechanism of organometallic reactions through the collaboration of theoretical calculation with experimental study. The promotion of theoretical study on experimental development could be summarized into “3D,” i.e. description, design, and direction. Based on the data obtained from experimental study, detailed descriptions of the organometallic reaction mechanisms could be fulfilled using theoretical calculation. The mechanistic study then provides further theoretical guidance for the rational design of new reactions, which points out the direction of experimental development.
Over recent decades, massive experimental and theoretical investigations on organometallic catalysis have been reported. In those works, theoretical studies have been proved to be an indispensable technique for modern organic chemistry. Consequently, this book is written to summarize and generalize the theoretical advances in the mechanistic study of organometallic catalysis. This book comprises two parts, which are the general overview of organometallic catalysis and the computational studies of reaction mechanisms classified by transition metals. I hope this book could inspire the mechanistic studies of complex reactions for theoretical chemists, and enable a better understanding of reaction mechanisms for experimental chemists.
29 July 2020
Yu LanZhengzhou, P. R. China
Part ITheoretical View of Organometallic Catalysis
It is time to write a book on computational organometallic chemistry.
The first part of this book can be considered as the introduction to computational organometallic chemistry. It is a long history since organometallic catalysis has been applied in organic synthesis; however, the mechanism of those reactions is too complicated to understand. Indeed, computational chemistry provided a powerful tool to reveal the mechanism of organometallic reactions. During recent two decades, the combination of computational chemistry and organometallic chemistry has made a series of progress in mechanistic studies, which has led to a new discipline, computational organometallic chemistry.
The first part would be composed of three chapters. In Chapter 1, a brief history of organometallics is given to reveal the significance of this chemistry. Computational chemistry, especially computational methods, is discussed in Chapter 2, which would be used in mechanism study of organometallic catalysis. Detailed processes for the familiar elementary reactions in organometallic catalysis discovered by theoretical calculations are summarized in Chapter 3.
1Introduction of Computational Organometallic Chemistry
This chapter provides a brief introduction of computational organometallic chemistry, which usually focuses on the reaction mechanism of homogeneous organometallic catalysis.
1.1 Overview of Organometallic Chemistry
In this section, the historical footprint of organometallic chemistry is concisely given, which would help the readers better understand the role of computation in the mechanistic study of organometallic chemistry.
1.1.1 General View of Organometallic Chemistry
Creating new material is always entrusted with the important responsibility for the development of human civilization [1–3]. In particular, synthetic chemistry becomes a powerful tool for chemists, as it exhibits great value for the selective construction of new compounds [4–8]. Various useful molecules could be prepared by the strategies of synthetic chemistry, which provides material foundation, technological support, and drive force for science [9–20]. Synthetic chemistry is also the motivating force for the progress of material science, pharmaceutical science, energy engineering, agriculture, and electronics industry [21–41]. In this area, organic synthesis reveals broad interests from a series of research fields, which could target supply to multifarious functional molecules.
The synthetic organic chemistry usually focuses on “carbon” to widen related research, which could afford various strategies for the building of molecular framework, functional group transformations, and controlling stereochemistry in more sophisticated molecules [9, 22, 42–50]. Therefore, selective formation of new covalent bond between carbon atom and some other atom involving nitrogen, oxygen, sulfur, halogen, boron, and phosphorus becomes one of the most important aims for synthetic organic chemistry. In particular, nucleophiles and electrophiles are important for the construction of new covalent bonds.
A nucleophile, which is a molecule with formal lone‐pair electrophiles, can donate two electrons to its reaction partner for the formation of new covalent bond. Alternatively, an electrophile, which is a molecule with formal unoccupied orbitals, can accept two electrons from its partner for the formation of new covalent bond. Thereinto, coupling reactions could be categorized as redox‐neutral cross‐coupling with an electrophile and a nucleophile, oxidative coupling with two nucleophiles, and reductive coupling with two electrophiles (Scheme 1.1).
Scheme 1.1 Cross‐coupling reactions with nucleophiles and electrophiles.
In organic chemistry, the nucleophile is an electron‐rich molecule that contains a lone pair of electrons or a polarized bond, the heterolysis of which also could yield a lone pair of electrons (Scheme 1.2). According to this concept, organometallic compounds, alcohols, halides, amines, and phosphines with a lone pair of electrons are nucleophiles. Some nonpolar π bonds, including olefins and acetylenes, which could donate the π‐bonding electrons, are often considered to be nucleophiles. Moreover, the C—H bonds of hydrocarbons can be considered to be nucleophiles because the electronegativity of carbon is higher than that of hydrogen, which could deliver a proton to form a formal carbon anion. Correspondingly, the electrophile is an electron‐deficient molecule that contains unoccupied orbitals or low‐energy antibonding molecular orbital, which could accept the electrons from nucleophiles. In this chemistry, cationic carbons, which usually come from the heterolysis of carbon—halogen bonds, are electrophile. Polar π bonds, including carbonyl compounds and imines, also could be considered to be electrophile, which involve a low‐energy π antibond. Interestingly, Fisher‐type singlet carbene has an electron pair filling one sp2 hybrid orbital and an unoccupied p orbital, which could be considered to be either nucleophile or electrophile in coupling reactions.
Scheme 1.2 Some selected examples of nucleophiles.
Superficially, at least, the reaction between nucleophile and electrophile could construct a covalent bond undoubtedly. However, the familiar nucleophiles and electrophiles, used in cross‐coupling reactions, are usually inactive, which could not react with each other rapidly. Moreover, when more active nucleophiles and electrophiles are used in coupling reactions, it would become out of control, which would not selectively afford target products. In effect, introducing transition metal catalysis can perfectly solve this problem. The appropriate transition metal can be employed to selectively activate the nucleophiles and electrophiles and stabilize some others, which led to a specially appointed cross‐coupling reaction.
High‐valence transition metal can obtain electrons from nucleophile, which led to the transformation of nucleophile into electrophile. The newly generated electrophile can couple with other nucleophiles to form covalent bond, which is named oxidative coupling reaction [51–53]. Meanwhile, the reduced transition metal can be oxidized by exogenous oxidant for regeneration. Correspondingly, low‐valence transition metal can donate electrons to electrophile leading to the transformation of electrophile into nucleophile, which can react with another electrophile to form covalent bond. Accordingly, it is named reductive coupling reaction. The oxidized transition metal also can be reduced by exogenous reductant.
The d orbital of some transition metals could be filled by unpaired electrons, which led to a unique catalytic activity in radical‐involved reactions. The homolytic cleavage of transition metal–carbon (or some other atoms) bond is an efficient way for the generation of a radical species, which can promote further transformations. On the other hand, free radical can react with some transition metal leading to the stabilization of radical, which can cause further radical transformations [54–57]. Moreover, nucleophiles and electrophiles, activated by transition metals, also can react with radical to form new covalent bonds.
Although there is no electron barrier due to the appropriate symmetry of frontier molecular orbitals, a great deal of uncatalyzed pericyclic reactions would occur under harsh reaction conditions, which could be often attributed to the low‐energy level of highest occupied molecular orbitals (HOMOs) and high‐energy level of lowest unoccupied molecular orbitals (LUMOs) in reacting partners. Transition metals can play as a Lewis acid, which could significantly reduce the LUMO of coordinated organic moiety. Therefore, it has been widely adopted to catalyze pericyclic reactions, which leads to moderate reaction conditions and adjustable selectivity [58–62]. Moreover, the node of d orbital can change the symmetry of a conjugative compound, which involves a transition metal. Therefore, transition metal itself also could participate in a pericyclic reaction to reveal unique catalytic activity.
