Contemporary carbene chemistry (Hoboken, 2014). - ОГЛАВЛЕНИЕ / CONTENTS
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ОбложкаContemporary carbene chemistry / ed. by R.A.Moss, M.P.Doyle. - Hoboken: Wiley, 2014. - xxi, 566 p.: ill. - (Wiley series of reactive intermediates in chemistry and biology; vol.7). - Incl. bibl. ref. - Ind.: p.552-566. - ISBN 978-1-118-23795-3
 

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Оглавление / Contents
 
PREFACE TO SERIES ............................................ xiii
PREFACE ........................................................ xv
CONTRIBUTORS .................................................. xix

PART 1  PROPERTIES AND REACTIONS OF CARBENES .................... 1
1    Carbene Stability .......................................... 3
     Scott Gronert, James R. Keeffe, and Rory A. More
     O'Ferrall
1.1  Introduction ............................................... 3
1.2  Background ................................................. 4
     1.2.1  Measures of Carbene Stability ....................... 4
     1.2.2  Bonding and Orbital Interactions in Carbenes ........ 6
     1.2.3  Determining Carbene Stability ....................... 8
1.3  Carbene Stability ......................................... 11
     1.3.1  Hydrocarbon-Substituted Carbenes ................... 11
     1.3.2  Substituted Phenylcarbenes ......................... 16
     1.3.3  Heteroatom-Substituted Carbenes .................... 20
     1.3.4  Conjugated Heterocyclic Carbenes ................... 24
     1.3.5  Carbenes with Other Electron-Withdrawing Groups .... 27
     1.3.6  Carbenes versus Ylides ............................. 29
1.4  Correlations Involving Carbene Stability .................. 30
     1.4.1  CSE versus Singlet-Triplet Gap ..................... 30
     1.4.2  CSE(Singlet) versus Proton Affinities .............. 31
     1.4.3  CSE(Singlet) versus Carbene Reaction Rates ......... 32
1.5 Conclusion and Outlook ..................................... 35
     Suggested Reading ......................................... 35
     References ................................................ 36

2    Stable Carbenes ........................................... 40
     Jonathan P. Moerdyk and Christopher W. Bielawski
2.1  Introduction .............................................. 40
2.2  Types of Stable Carbenes .................................. 41
     2.2.1  Push-Push Carbenes ................................. 42
     2.2.2  Push-Pull Carbenes ................................. 48
     2.2.3  Abnormal Carbenes .................................. 49
2.3  Spectroscopic Characteristics ............................. 50
2.4  Chemical Reactivity ....................................... 52
     2.4.1  Heteroallenes/Electrophilic Traps .................. 55
     2.4.2  Lewis Acids: Boryl Compounds ....................... 56
     2.4.3  Alkenes, Alkynes, and Nitriles ..................... 56
     2.4.4  Carbon Monoxide and Isonitriles .................... 59
     2.4.5  X-H Activation ..................................... 60
     2.4.6  Homodiatomic Bond Activation ....................... 63
     2.4.7  Elemental Дtiotropes and other Reactive Species .... 65
2.5  Conclusions and Outlook ................................... 65
     Suggested Reading ......................................... 67
     References ................................................ 67

3    Acid-Base Chemistry of Carbenes ........................... 75
     Ann Marie C. O'Donoghue and Richard S. Massey
3.1  Introduction .............................................. 75
3.2  Solution pKas of the Conjugate Acids of Carbenes .......... 76
     3.2.1  Experimental Methods in Aprotic Solvents ........... 77
     3.2.2  Experimental Methods in Aqueous Solution ........... 80
     3.2.3  Substituent Effects on рКa ......................... 85
     3.2.4  Solvent Effects on pKa ............................. 91
3.3  Gas-Phase Basicities and Proton Affinities of Carbenes .... 92
     3.3.1  Experimental Methods ............................... 93
     3.3.2  Heteroatom-Stabilized Carbenes ..................... 94
     3.3.3  Alkyl-and Aryl-Substituted Carbenes ............... 100
     3.3.4  Halocarbenes ...................................... 102
3.4  Conclusion and Outlook ................................... 103
     Suggested Reading ........................................ 104
     References ............................................... 104

4    Computational Methods for the Study of Carbenes and
     their Excited States ..................................... 107
     Hoi Ling Luk, Shubham Vyas, and Christopher M. Hadad
4.1  Introduction ............................................. 107
4.2  Carbenes ................................................. 109
4.3  Rearrangement in Excited States (RIES) ................... 111
4.4  Advances in Computational Investigations of Carbenes ..... 115
     4.4.1  Configuration Interaction ......................... 117
     4.4.2  Complete Active Space Self-Consistent Field
            (CASSCF) Theory ................................... 118
     4.4.3  Coupled-Cluster Theory with Resolution-of-the-
            Identity Approximation (RI-CC2) ................... 121
     4.4.4  Time-Dependent Density Functional Theory
            (TD-DFT) .......................................... 121
     4.4.5  Molecular Dynamics (MD) ........................... 123
4.5  Theoretical Studies of the Photochemistry of Carbene
     Precursors ............................................... 123
4.6  Conclusion and Outlook ................................... 127
     Suggested Reading ........................................ 128
     References ............................................... 128

5    Dynamics in Carbene Reactions ............................ 131
     Dina C. Merrer, K.N. Houk, and Lai Xu
5.1  Introduction ............................................. 131
     5.1.1  Carbenes .......................................... 131
     5.1.2  Nonstatistical Reaction Dynamics .................. 133
5.2  Dynamics of Carbene Cycloadditions to Alkenes and
     Alkynes .................................................. 136
     5.2.1  Carbene Additions to Unstrained Alkenes ........... 136
     5.2.2  Carbene Additions to Strained π Systems ........... 144
     5.2.3  Carbene Additions to Strained a Systems ........... 152
5.3  Dynamics of Other Carbene-Mediated Reactions ............. 153
     5.3.1  Wolff Rearrangement ............................... 153
     5.3.2  Photochemical Carbene Formation ................... 156
5.4  Conclusion and Outlook ................................... 159
     Suggested Reading ........................................ 159
     References ............................................... 160

6    Ultrafast Kinetics of Carbene Reactions .................. 166
     Gotard Burdzinski and Mathew S. Platz
6.1  Introduction ............................................. 166
6.2  Ultrafast UV-Vis Studies of the Intermolecular
     Reactivity of p-Biphenylylcarbene (BpCH) ................. 167
6.3  Rearrangements in the Excited State of the Carbene
     Precursor ................................................ 171
6.4  Dynamics of Carbene Vibrational Cooling and Solvation .... 173
6.5  Influence of Solvent on Carbene Intersystem Crossing
     Rates .................................................... 176
6.6  Electronically Excited (Open Shell) Singlet Carbenes ..... 179
6.7  Parent Phenyldiazirine—Mechanistic Aspects of Singlet
     Carbene Formation ........................................ 179
6.8  Influence of Halo-Substituent Electron-Donating
     Capacity on Diazirine Decay in the First Excited
     Singlet State ............................................ 183
6.9  The Influence of Excitation Wavelength on the
     Photochemistry of Diazirines ............................. 186
6.10 Conclusion and Outlook ................................... 189
     Suggested Reading ........................................ 190
     References ............................................... 191

7    Tunneling in the Reactions of Carbenes and Oxacarbenes ... 193
     Dennis Gerbig and Peter R. Schreiner
7.1  Introduction: Light- and Heavy-Atom Tunneling ............ 193
7.2  Alkyl- and Halocarbenes .................................. 197
     7.2.1  Cyclopropylcarbenes ............................... 197
     7.2.2  Ethylidene and Phenylmethylcarbene ................ 200
     7.2.3  Methylchlorocarbene and Benzylchlorocarbene ....... 201
     7.2.4  tert-Butylchlorocarbene ........................... 202
     7.2.5  1-Methylcyclobutylfluorocarbene ................... 202
     7.2.6  Noradamantylchlorocarbene ......................... 203
7.3  The Formose Reaction and Hydroxycarbenes ................. 203
     7.3.1  Hydroxymethylene .................................. 203
     7.3.2  Methylhydroxycarbene and Tunneling Control ........ 205
     7.3.3  Arylhydroxycarbenes ............................... 206
     7.3.4  Cyclopropylhydroxycarbene ......................... 209
7.4  Conclusion and Outlook ................................... 210
     Suggested Reading ........................................ 211
     References ............................................... 211

8    Carbodicarbenes .......................................... 216
     Gernot Frenking and Ralf Tonner
8.1  Introduction ............................................. 216
8.2  Carbodicarbenes with N-Heterocyclic Ligands C(NHC)2 ...... 218
8.3  Tetraaminoallenes and "Hidden" Carbodicarbenes ........... 225
8.4  Bent Allenes ............................................. 228
8.5  Related Compounds ........................................ 233
8.6  Conclusion and Outlook ................................... 234
     Suggested Reading ........................................ 234
     References ............................................... 234

9    Catalytic Reactions with N-Mesityl-Substituted
     A'-Heterocyclic Carbenes ................................. 237
     Jessada Mahatthananchai and Jeffrey W. Bode
9.1  Introduction ............................................. 237
     9.1.1  Historical Background ............................. 238
     9.1.2  State of the Art Prior to 2004 .................... 238
     9.1.3  N-Mesityl Catalysts as the Key Innovation ......... 239
9.2  The N-Mesityl Group: A Mechanistic Aspect ................ 242
     9.2.1  Catalytic Generation of Reactive Species via
            N-Mesityl NHCs .................................... 242
     9.2.2  The Kinetic Effect of the N-Mesityl Group ......... 243
9.3  NHC Catalysis by Class of Reactive Intermediates ......... 246
     9.3.1  Acyl Anion Equivalent ............................. 246
     9.3.2  Homoenolate Equivalent ............................ 248
     9.3.3  Enolate Equivalent ................................ 254
     9.3.4  Activated Carboxylate Equivalent .................. 257
     9.3.5  α,β-Unsaturated Activated Carboxylate
            Equivalent ........................................ 264
9.4  Conclusion and Outlook ................................... 268
     Suggested Reading ........................................ 268
     References ............................................... 268

10   Supramolecular Carbene Chemistry ......................... 274
     Udo H. Brinker, Jean-Luc Mieusset, and Murray
     G. Rosenberg
10.1 Introduction ............................................. 274
10.2 Types of Hosts Used in Supramolecular Carbene Chemistry .. 276
     10.2.1 Cyclodextrins ..................................... 276
     10.2.2 Hemicarcerands .................................... 276
     10.2.3 Resorcin[4]arene-Based Cavitands .................. 278
     10.2.4 Octa Acid ......................................... 278
     10.2.5 Cucurbit[n]urils .................................. 278
     10.2.6 Zeolites .......................................... 280
10.3 Choosing the Right Carbene Guest ......................... 283
10.4 Diazirines as Suitable Supramolecular Carbene
     Precursors ............................................... 285
10.5 Architecture of the Guest@Host Complex ................... 287
10.6 Case Studies ............................................. 291
     10.6.1 Carbenes with Available 1,2-H Shifts .............. 291
     10.6.2 (2-[l,3-Dioxolan-2-yl]phenyl)(4-phenylphenyl)-
            carbene ........................................... 294
     10.6.3 4-Oxocyclohexa-2,5-dienylidene .................... 295
     10.6.4 Dichlorocarbene ................................... 296
     10.6.5 Adamantylidene .................................... 296
     10.6.6 3-Oxobicyclo[3.2.1]octan-8-ylidene ................ 302
     10.6.7 endo-3-Hydroxybicyclo[3.2.1]octan-8-ylidene ....... 304
     10.6.8 Ring Fragmentation and Expansion .................. 305
     10.6.9 Aryl(halo)carbenes ................................ 308
     10.6.10 Fluoro(phenoxy)carbene ........................... 312
     10.6.11 Persistent Triplet Carbenes ...................... 312
10.7 Conclusion and Outlook ................................... 313
     Acknowledgments .......................................... 315
     Suggested Reading ........................................ 315
     References ............................................... 315

PART 2  METAL CARBENES ........................................ 325
11   Modern Lithium Carbenoid Chemistry ....................... 327
     Vita Capriati
11.1 Introduction ............................................. 327
11.2 Structural Features of Lithium Carbenoids ................ 328
11.3 Lithium Halide Carbenoids ................................ 329
     11.3.1 Thermal and Kinetic Stability ..................... 329
     11.3.2 Configurational Stability and Stereochemistry
            of the Coupling Reactions with Electrophiles ...... 331
11.4 Structure-Reactivity Relationships ....................... 342
11.5 Lithium-Oxygen Carbenoids ................................ 344
11.6 Lithium-Nitrogen Carbenoids .............................. 352
11.7 Conclusion and Outlook ................................... 355
     Suggested Reading ........................................ 357
     References ............................................... 357

12   Rhodium Carbenes ......................................... 363
     Huw M.L. Davies and Brendan T. Parr
12.1 Introduction ............................................. 363
12.2 Overview of Rhodium-Carbenoid Intermediates and Chiral
     Catalysts ................................................ 364
12.3 Enantioselective Cyclopropanation ........................ 367
12.4 Cascade Sequences Initiated by Rhodium-Catalyzed
     Cyclopropanation ......................................... 370
12.5 Enantioselective Cyclopropenation ........................ 373
12.6 C-H Functionalization By Carbenoid-Induced C-H
     Insertion ................................................ 375
12.7 Combined C-H Activation/Cope Rearrangement (CHCR) ........ 380
12.8 Formation and Reactions of Rhodium-Bound Ylides .......... 383
12.9 Vinylogous Reactions of Rhodium-Vinylcarbenoids .......... 392
12.10 Conclusions and Future Outlook .......................... 397
     Suggested Reading ........................................ 397
     References ............................................... 398

13   Ruthenium Carbenes ....................................... 404
     Steven T. Diver and Jonathan M. French
13.1 Introduction ............................................. 404
13.2 Improved Mechanistic Understanding ....................... 405
     13.2.1 Background ........................................ 406
     13.2.2 Identification of Ruthenacyclobutane
            Intermediates in Alkene Metathesis ................ 410
     13.2.3 Conformational Dynamics "Windshield Wipering" ..... 412
13.3 Catalyst Development ..................................... 413
     13.3.1 Development of Phosphine-Free Catalysts ........... 413
     13.3.2 Decomposition of the Grubbs' Complex .............. 417
13.4 Achieving Selectivity in Alkene Metathesis ............... 424
     13.4.1 Enantioselective Metathesis with Ruthenium
            Carbenes .......................................... 424
     13.4.2 Site Selectivity Using Relay Ring-Closing
            Metathesis ........................................ 426
     13.4.3 Z-Selective Alkene Metathesis ..................... 429
13.5 Applications ............................................. 432
     13.5.1 Selected Examples of Alkene Metathesis in
            the Total Synthesis of Natural Products ........... 432
     13.5.2 Applications of Metathesis in Aqueous Systems ..... 438
     13.5.3 Applications in Diversity-Oriented Synthesis ...... 441
13.6 Conclusion and Outlook ................................... 444
     Suggested Reading ........................................ 445
     References ............................................... 446

14   Nucleophilic Carbenes of the Chromium Triad .............. 452
     Zachary J. Tonzetich
14.1 Introduction ............................................. 452
     14.1.1 Discovery ......................................... 453
     14.1.2 Spectroscopic Properties .......................... 455
     14.1.3 Metathesis Reactivity ............................. 455
14.2 Chromium Carbenes ........................................ 457
     14.2.1 Cr(VI) Carbenes ................................... 457
     14.2.2 Nucleophilic Cr(III) Carbenes ..................... 459
     14.2.3 Supported Cr(IV) Carbenes ......................... 459
14.3 Molybdenum Carbenes ...................................... 460
     14.3.1 Mo(VI) Imido-Alkylidene-bis-Alkoxide Compounds .... 461
     14.3.2 Mo(VI) Imido-Alkylidene Pyrrolide Compounds ....... 468
     14.3.3 Other Nucleophilic Mo Carbenes .................... 471
     14.3.4 Supported Mo Alkylidenes .......................... 473
14.4 Tungsten Carbenes ........................................ 476
     14.4.1 W(VI) Imido-Alkylidene-bis-Alkoxide Compounds ..... 476
     14.4.2 W(VI) Imido-Alkylidene Pyrrolide Compounds ........ 477
     14.4.3 Other Nucleophilic Tungsten Carbenes .............. 480
14.5 Conclusions and Outlook .................................. 484
     Suggested Reading ........................................ 485
     References ............................................... 485

15   Cobalt-Mediated Carbene Transfer Reactions ............... 491
     Xin Cui and X. Peter Zhang
15.1 Introduction ............................................. 491
15.2 Cobalt-Catalyzed Cyclopropanation Reactions .............. 494
     15.2.1 Cobalt Dioximato and Cobalt Ketoiminato
            Catalysts ......................................... 494
     15.2.2 Cobalt Salen Catalysts ............................ 496
     15.2.3 Cobalt Porphyrin Catalysts ........................ 501
     15.2.4 Cobalt Catalysts with Other Supporting Ligands .... 512
     15.2.5 Mechanistic Studies ............................... 514
15.3 Other Cobalt-Catalyzed Carbene Transfer Reactions ........ 517
     15.3.1 Cyclopropenation .................................. 517
     15.3.2 Carbonylation ..................................... 518
     15.3.3 Olefination ....................................... 519
15.4 Conclusion and Outlook ................................... 520
     Acknowledgments .......................................... 522
     Suggested Reading ........................................ 522
     References ............................................... 522

16   Gold Carbenes ............................................ 526
     Liming Zhang
16.1 Introduction ............................................. 526
16.2 Nature of the Au-Carbon Double Bond ...................... 528
     16.2.1 Experimental Studies .............................. 528
     16.2.2 DFT Calculations .................................. 529
16.3 Generation and Reactions of Gold Carbenes ................ 530
     16.3.1 Gold Carbenes with Dative or Alkyl Substituents ... 530
     16.3.2 Generation and Reactions of α-Oxo Gold Carbenes ... 534
     16.3.3 Generation and Reactions of α-Imino Gold
            Carbenes .......................................... 542
     16.3.4 Generation and Reactivities of Gold Carbenes
            via Carbene Transfer .............................. 545
     16.3.5 Generation and Reactivities of 1,3-Dipolar
            Gold Carbenes from Allenes ........................ 545
16.4 Conclusion and Outlook ................................... 547
     Suggested Reading ........................................ 548
     References ............................................... 548

Index ......................................................... 552


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