Computational Methods in Organometallic Catalysis

Dr. Yu Lan, Distinguished Professor of Henan Province, is a part of the faculty of Zhengzhou University, China, and a 2016 recipient of the Chinese Chemical Society Award for Outstanding Yong Chemist. His current research focus is on theoretical study of the mechanism and selectivity for transition-metal catalysis.

• Foreword xvPreface xviiPart I Theoretical View of Organometallic Catalysis 11 Introduction of Computational Organometallic Chemistry 31.1 Overview of Organometallic Chemistry 31.1.1 General View of Organometallic Chemistry 31.1.2 A Brief History of Organometallic Chemistry 61.2 Using Computational Tool to Study the Organometallic ChemistryMechanism 81.2.1 Mechanism of Transition Metal Catalysis 81.2.2 Mechanistic Study of Transition Metal Catalysis by Theoretical Methods 10References 132 Computational Methods in Organometallic Chemistry 192.1 Introduction of Computational Methods 192.1.1 The History of Quantum Chemistry Computational Methods 192.1.2 Post-HF Methods 212.2 Density Functional Theory (DFT) Methods 232.2.1 Overview of Density Functional Theory Methods 232.2.2 Jacob’s Ladder of Density Functionals 252.2.3 The Second Rung in “Jacob’s Ladder” of Density Functionals 252.2.4 The Third Rung in “Jacob’s Ladder” of Density Functionals 262.2.5 The Fourth Rung in “Jacob’s Ladder” of Density Functionals 262.2.6 The Fifth Rung in “Jacob’s Ladder” of Density Functionals 262.2.7 Correction of Dispersion Interaction in Organic Systems 272.3 Basis Set and Its Application in Mechanism Studies 292.3.1 General View of Basis Set 292.3.2 Pople’s Basis Sets 302.3.3 Polarization Functions 312.3.4 Diffuse Functions 312.3.5 Correlation-Consistent Basis Sets 312.3.6 Pseudo Potential Basis Sets 322.4 Solvent Effect 332.5 How to Choose a Method in Computational Organometallic Chemistry 342.5.1 Why DFT Method Is Chosen 342.5.2 How to Choose a Density Functional 342.5.3 How to Choose a Basis Set 362.6 Revealing a Mechanism for An Organometallic Reaction by Theoretical Calculations 372.7 Overview of Popular Computational Programs 372.8 The Limitation of Current Computational Methods 402.8.1 The Accuracy of DFT Methods 402.8.2 Exact Solvation Effect 412.8.3 Evaluation of Entropy Effect 412.8.4 The Computation of Excited State and High Spin State 412.8.5 Speculation on the Reaction Mechanism 41References 423 Elementary Reactions in Organometallic Chemistry 513.1 General View of Elementary Reactions in Organometallic Chemistry 513.2 Coordination and Dissociation 523.2.1 Coordination Bond and Coordination 523.2.2 Dissociation 553.2.3 Ligand Exchange 573.3 Oxidative Addition 593.3.1 Concerted Oxidative Addition 603.3.2 Substitution-type Oxidative Addition 623.3.3 Radical-type Addition 673.3.4 Oxidative Cyclization 683.4 Reductive Elimination 703.4.1 Concerted Reductive Elimination 713.4.2 Substitution-type Reductive Elimination 733.4.3 Radical-Substitution-type Reductive Elimination 743.4.4 Bimetallic Reductive Elimination 753.4.5 Eliminative Reduction 783.5 Insertion 783.5.1 1,2-Insertion 793.5.2 1,1-Insertion 803.5.3 Conjugative Insertion 833.5.4 Outer-Sphere Insertion 843.6 Elimination 863.6.1 β-Elimination 863.6.2 α-Elimination 903.7 Transmetallation 923.7.1 Concerted Ring-Type Transmetallation 923.7.2 Transmetallation Through Electrophilic Substitution 983.7.3 Stepwise Transmetallation 993.8 Metathesis 1003.8.1 σ-Bond Metathesis 1003.8.2 Olefin Metathesis 1023.8.3 Alkyne Metathesis 106References 106Part II On the Mechanism of Transition-metal-assisted Reactions 1254 Theoretical Study of Ni-Catalysis 1274.1 Ni-Mediated C—H Bond Activation 1284.1.1 Ni-Mediated Arene C—H Activation 1284.1.2 Ni-Mediated Aldehyde C—H Activation 1324.2 Ni-Mediated C—Halogen Bond Cleavage 1334.2.1 Concerted Oxidative Addition of C—Halogen Bond 1334.2.2 Radical-Type Substitution of C—Halogen Bond 1354.2.3 C—Halogen Bond Cleavage by β-Halide Elimination 1374.2.4 Nucleophilic Substitution of C—Halogen Bond 1394.3 Ni-Mediated C—O Bond Activation 1404.3.1 Ether C—O Bond Activation 1404.3.2 Ester C—O Bond Activation 1424.4 Ni-Mediated C—N Bond Cleavage 1484.5 Ni-Mediated C—C Bond Cleavage 1514.5.1 C—C Single Bond Activation 1514.5.2 C=C Double Bond Activation 1524.6 Ni-Mediated Unsaturated Bond Activation 1534.6.1 Oxidative Cyclization with Unsaturated Bonds 1534.6.2 Electrophilic Addition of Unsaturated Bonds 1564.6.3 Unsaturated Compounds Insertion 1574.6.4 Nucleophilic Addition of Unsaturated Bonds 1594.7 Ni-Mediated Cyclization 1604.7.1 Ni-Mediated Cycloadditions 1614.7.2 Ni-Mediated Ring Substitutions 1634.7.3 Ni-Mediated Ring Extensions 166References 1685 Theoretical Study of Pd-Catalysis 1815.1 Pd-Catalyzed Cross-coupling Reactions 1825.1.1 Suzuki–Miyaura Coupling 1835.1.2 Negishi Coupling 1865.1.3 Stille Coupling 1895.1.4 Hiyama Coupling 1905.1.5 Heck–Mizoroki Reaction 1925.2 Pd-Mediated C—Hetero Bond Formation 1965.2.1 C—B Bond Formation 1965.2.2 C—S Bond Formation 1975.2.3 C—I Bond Formation 2005.2.4 C—Si Bond Formation 2015.3 Pd-Mediated C—H Activation Reactions 2045.3.1 Chelation-Free C(sp3)—H Activation 2065.3.2 Chelation-Free C(sp2)—H Activation 2085.3.3 Coordinative Chelation-Assisted ortho- C(aryl)—H Activation 2105.3.4 Covalent Chelation-Assisted ortho- C(aryl)—H Activation 2125.3.5 Chelation-Assisted meta- C(aryl)—H Activation 2145.3.6 Coordinative Chelation-Assisted C(sp3)—H Activation 2165.3.7 Covalent Chelation-Assisted C(sp3)—H Activation 2165.3.8 C—H Bond Activation Through Electrophilic Deprotonation 2195.3.9 C—H Bond Activation Through σ-Complex-Assisted Metathesis 2215.3.10 C—H Bond Activation Through Oxidative Addition 2235.4 Pd-Mediated Activation of Unsaturated Molecules 2245.4.1 Alkene Activation 2255.4.2 Alkyne Activation 2255.4.3 Enyne Activation 2265.4.4 Imine Activation 2295.4.5 CO Activation 2295.4.6 Isocyanide Activation 2315.4.7 Carbene Activation 2315.5 Allylic Pd Complex 2345.5.1 Formation from Allylic Oxidative Addition 2355.5.2 Formation from Allylic Nucleophilic Substitution 2365.5.3 Formation from the Nucleophilic Attack onto Allene 2375.5.4 Formation from Allylic C—H Activation 2375.5.5 Formation from Allene Insertion 238References 2396 Theoretical Study of Pt-Catalysis 2576.1 Mechanism of Pt-Catalyzed C—H Activation 2586.1.1 Oxidative Addition of C—H Bond 2596.1.2 Electrophilic Dehydrogenation 2596.1.3 Carbene Insertion into C—H Bonds 2616.2 Mechanism of Pt-Catalyzed Alkyne Activation 2646.2.1 Nucleophilic Additions 2646.2.2 Cyclopropanation 2666.2.3 Oxidative Cycloaddition 2686.3 Mechanism of Pt-Catalyzed Alkene Activation 2706.3.1 Hydroamination of Alkenes 2706.3.2 Hydroformylation of Alkenes 2726.3.3 Isomerization of Cyclopropenes 273References 2747 Theoretical Study of Co-Catalysis 2897.1 Co-Mediated C—H Bond Activation 2897.1.1 Hydroarylation of Alkenes 2917.1.2 Hydroarylation of Allenes 2937.1.3 Hydroarylation of Alkynes 2947.1.4 Hydroarylation of Nitrenoid 2967.1.5 Oxidative C—H Alkoxylation 2977.2 Co-Mediated Cycloadditions 2977.2.1 Co-Mediated Pauson–Khand Reaction 2987.2.2 Co-Catalyzed [4+2] Cyclizations 2997.2.3 Co-Catalyzed [2+2+2] Cyclizations 2997.2.4 Co-Catalyzed [2+2] Cyclizations 3007.3 Co-Catalyzed Hydrogenation 3017.3.1 Hydrogenation of Carbon Dioxide 3017.3.2 Hydrogenation of Alkenes 3047.3.3 Hydrogenation of Alkynes 3067.4 Co-Catalyzed Hydroformylation 3077.4.1 Direct Hydroformylation by H2 and CO 3087.4.2 Transfer Hydroformylation 3097.5 Co-Mediated Carbene Activation 3107.5.1 Arylation of Carbene 3107.5.2 Carboxylation of Carbene 3127.6 Co-Mediated Nitrene Activation 3137.6.1 Aziridination of Olefins 3147.6.2 Amination of Isonitriles 3147.6.3 Amination of C—H Bonds 315References 3178 Theoretical Study of Rh-Catalysis 3298.1 Rh-Mediated C—H Activation Reactions 3308.1.1 Rh-Catalyzed Arylation of C—H Bond 3308.1.2 Rh-Catalyzed Alkylation of C—H Bond 3328.1.3 Rh-Catalyzed Alkenylation of C—H Bond 3358.1.4 Rh-Catalyzed Amination of C—H Bond 3388.1.5 Rh-Catalyzed Halogenation of C—H Bond 3408.2 Rh-Catalyzed C—C Bond Activations and Transformations 3418.2.1 Strain-driven Oxidative Addition 3418.2.2 The Carbon—Cyano Bond Activation 3428.2.3 β-Carbon Elimination 3438.3 Rh-Mediated C—Hetero Bond Activations 3438.3.1 C—N Bond Activation 3448.3.2 C—O Bond Activation 3458.4 Rh-Catalyzed Alkene Functionalizations 3458.4.1 Hydrogenation of Alkene 3468.4.2 Diboration of Alkene 3478.5 Rh-Catalyzed Alkyne Functionalizations 3498.5.1 Hydroacylation of Alkynes 3498.5.2 Hydroamination of Alkynes 3498.5.3 Hydrothiolation of Alkynes 3518.5.4 Hydroacetoxylation of Alkynes 3518.6 Rh-Catalyzed Addition Reactions of Carbonyl Compounds 3528.6.1 Hydrogenation of Ketones 3528.6.2 Hydrogenation of Carbon Dioxide 3538.6.3 Hydroacylation of Ketones 3538.7 Rh-Catalyzed Carbene Transformations 3548.7.1 Carbene Insertion into C—H Bonds 3548.7.2 Arylation of Carbenes 3578.7.3 Cyclopropanation of Carbenes 3588.7.4 Cyclopropenation of Carbenes 3598.8 Rh-Catalyzed Nitrene Transformations 3598.8.1 Nitrene Insertion into C—H Bonds 3608.8.2 Aziridination of Nitrenes 3618.9 Rh-Catalyzed Cycloadditions 3628.9.1 (3+2) Cycloadditions 3658.9.2 Pauson–Khand-type (2+2+1) Cycloadditions 3678.9.3 (5+2) Cycloadditions 3678.9.4 (5+2+1) Cycloadditions 369References 3699 Theoretical Study of Ir-Catalysis 3879.1 Ir-Catalyzed Hydrogenations 3879.1.1 Hydrogenation of Alkenes 3889.1.2 Hydrogenation of Carbonyl Compounds 3919.1.3 Hydrogenation of Imines 3939.1.4 Hydrogenation of Quinolines 3969.2 Ir-Catalyzed Hydrofunctionalizations 3979.2.1 Ir-Catalyzed Hydroaminations 3979.2.2 Ir-Catalyzed Hydroarylations 3979.2.3 Ir-Catalyzed Hydrosilylations 3999.3 Ir-Catalyzed Borylations 4019.3.1 Borylation of Alkanes 4029.3.2 Borylation of Arenes 4039.4 Ir-Catalyzed Aminations 4059.4.1 Amination of Alcohols 4059.4.2 Amination of Arenes 4079.5 Ir-Catalyzed C—C Bond Coupling Reactions 407References 40910 Theoretical Study of Fe-Catalysis 41910.1 Fe-Mediated Oxidations 42010.1.1 Alkane Oxidations 42010.1.2 Arene Oxidations 42210.1.3 Alkene Oxidations 42310.1.4 Oxidative Catechol Ring Cleavage 42510.2 Fe-Mediated Hydrogenations 42610.2.1 Hydrogenation of Alkenes 42710.2.2 Hydrogenation of Carbonyls 42910.2.3 Hydrogenation of Imines 43010.2.4 Hydrogenation of Carbon Dioxide 43010.3 Fe-Mediated Hydrofunctionalizations 43110.3.1 Hydrosilylation of Ketones 43110.3.2 Hydroamination of Allenes 43210.4 Fe-Mediated Dehydrogenations 43410.4.1 Dehydrogenation of Alcohols 43410.4.2 Dehydrogenation of Formaldehyde 43510.4.3 Dehydrogenation of Formic Acid 43510.4.4 Dehydrogenation of Ammonia-Borane 43710.5 Fe-Catalyzed Coupling Reactions 43810.5.1 C—C Cross-Couplings with Aryl Halide 43810.5.2 C—N Cross-Couplings with Aryl Halide 43810.5.3 C—C Cross-Couplings with Alkyl Halide 44110.5.4 Iron-Mediated Oxidative Coupling 441References 44111 Theoretical Study of Ru-Catalysis 45111.1 Ru-Mediated C—H Bond Activation 45211.1.1 Mechanism of the Ru-Mediated C—H Bond Cleavage 45211.1.2 Ru-Catalyzed C—H Bond Arylation 45611.1.3 Ru-Catalyzed ortho-Alkylation of Arenes 46011.1.4 Ru-Catalyzed ortho-Alkenylation of Arenes 46111.2 Ru-Catalyzed Hydrogenations 46411.2.1 Hydrogenation of Alkenes 46411.2.2 Hydrogenation of Carbonyls 46511.2.3 Hydrogenation of Esters 46611.2.4 Hydrodefluorination of Fluoroarenes 46711.3 Ru-Catalyzed Hydrofunctionalizations 46811.3.1 Hydroacylations 46911.3.2 Hydrocarboxylations 47011.3.3 Hydroborations 47111.4 Ru-Mediated Dehydrogenations 47211.4.1 Dehydrogenation of Alcohols 47311.4.2 Dehydrogenation of Formaldehyde 47311.4.3 Dehydrogenation of Formic Acid 47411.5 Ru-Catalyzed Cycloadditions 47511.5.1 Ru-Mediated (2+2+2) Cycloadditions 47511.5.2 Ru-Mediated Pauson–Khand Type (2+2+1) Cycloadditions 47811.5.3 Ru-Mediated Click Reactions 47811.6 Ru-Mediated Metathesis 48011.6.1 Ru-Mediated Intermolecular Olefin Metathesis 48211.6.2 Ru-Mediated Intramolecular Diene Metathesis 48411.6.3 Ru-Mediated Alkyne Metathesis 484References 48512 Theoretical Study of Mn-Catalysis 49912.1 Mn-Mediated Oxidation of Alkanes 50012.1.1 C—H Hydroxylations 50012.1.2 C—H Halogenations 50112.1.3 C—H Azidations 50112.1.4 C—H Isocyanations 50112.2 Mn-Mediated C—H Activations 50212.2.1 Electrophilic Deprotonation 50312.2.2 σ-Complex-Assisted Metathesis 50412.2.3 Concerted Metalation–Deprotonation 50512.3 Mn-Mediated Hydrogenations 50712.3.1 Hydrogenation of Carbon Dioxide 50712.3.2 Hydrogenation of Carbonates 50812.4 Mn-Mediated Dehydrogenations 51012.4.1 Dehydrogenation of Alcohols 51012.4.2 Dehydrogenative Couplings 511References 51213 Theoretical Study of Cu-Catalysis 51713.1 Cu-Mediated Ullmann Condensations 51813.1.1 C—N Bond Couplings 52013.1.2 C—O Bond Couplings 52213.1.3 C—F Bond Couplings 52213.2 Cu-Mediated Trifluoromethylations 52413.2.1 Trifluoromethylations Through Cross-Coupling 52413.2.2 Trifluoromethylations Through Oxidative Coupling 52413.2.3 Radical-Type Trifluoromethylations 52513.3 Cu-Mediated C—H Activations 52713.3.1 C—H Arylations 52713.3.2 C—H Aminations 52913.3.3 C—H Hydroxylation 53113.3.4 C—H Etherifications 53213.4 Cu-Mediated Alkyne Activations 53313.4.1 Azide–Alkyne Cycloadditions 53313.4.2 Nucleophilic Attack onto Alkynes 53513.4.3 Alkynyl Cu Transformations 53613.5 Cu-Mediated Carbene Transformations 53913.5.1 [2+1] Cycloadditions with Alkenes 53913.5.2 Carbene Insertions 54113.5.3 Rearrangement of Carbenes 54213.6 Cu-Mediated Nitrene Transformations 54213.6.1 [2+1] Cycloadditions with Alkenes 54313.6.2 Amination of Nitrenes 54313.6.3 Nitrene Insertions 54413.7 Cu-Catalyzed Hydrofunctionalizations 54513.7.1 Hydroborylations 54713.7.2 Hydrosilylation 54713.7.3 Hydrocarboxylations 54813.8 Cu-Catalyzed Borylations 54913.8.1 Borylation of Alkenes 55113.8.2 Borylation of Alkynes 55213.8.3 Borylation of Carbonyls 553References 55414 Theoretical Study of Ag-Catalysis 56714.1 Ag-Mediated Carbene Complex Transformations 56814.1.1 Silver–Carbene Formation 56814.1.2 Carbene Insertion into C—Cl Bond 57214.1.3 Carbene Insertion into O—H Bond 57314.1.4 Nucleophilic Attack by Carbonyl Groups 57314.1.5 Carbene Insertion into C—H Bond 57414.2 Ag-Mediated Nitrene Transformations 57614.2.1 Silver–Nitrene Complex Formation 57714.2.2 Nucleophilic Attack by Unsaturated Bonds 58014.2.3 Nucleophilic Attack by Amines 58214.3 Ag-Mediated Silylene Transformations 58314.4 Ag-Mediated Alkyne Activations 58514.4.1 π-Activation of Alkynes 58614.4.2 C—H Activation of Alkynes 587References 58815 Theoretical Study of Au-Catalysis 59715.1 Au-Mediated Alkyne Activations 59815.1.1 Isomerization of Alkynes 59915.1.2 Nucleophilic Attack by Oxygen-Involved Nucleophiles 59915.1.3 Nucleophilic Attack by Nitrogen-Involved Nucleophiles 60215.1.4 Nucleophilic Attack by Arenes 60615.2 Au-mediated Alkene Activations 60715.2.1 Nucleophilic Addition of Alkenes 60715.2.2 Allylic Substitutions 60815.3 Au-mediated Allene Activations 60915.3.1 Hydroamination of Allenes 61015.3.2 Hydroalkoxylation of Allenes 61015.3.3 Cycloisomerization of Allenyl Ketones 61315.4 Au-mediated Enyne Transformations 61315.4.1 1,5-Enyne Cycloisomerizations 61415.4.2 1,6-Enyne Cycloisomerizations 61515.4.3 Allenyne Cycloisomerizations 61715.4.4 Conjugative Enyne Cycloisomerizations 617References 618Index 629