Chiral ferrocenes in asymmetric catalysis: synthesis and applications / ed. by Li-Xin Dai, Xue-Long Hou. - Weinheim: Wiley-VCH, 2010. - xvii, 414 p.: ill. - Incl. bibl. ref. - Ind.: p.397-414. - ISBN 978-3-527-32280-0  Место хранения:   031 | Институт катализа им. Г.К.Борескова CO РАН | Новосибирск

Оглавление / Contents

List of Contributors ........................................... XV 1 Introduction ................................................. 1 Li-Xin Dai and Xue-Long Hou 1.1 Foreword ................................................ 1 1.2 Planar Chirality of Ferrocenyl Ligands .................. 4 1.3 Derivatization of the Ferrocene Scaffold ................ 6 1.4 Stability, Rigidity and Bulkiness of the Ferrocene Scaffold ................................................ 9 1.5 Outlook ................................................ 10 References .................................................. 11 2 Stereoselective Synthesis of Planar Chiral Ferrocenes ....... 15 Wei-Ping Deng, Victor Snieckus, and Costa Metallinos 2.1 Introduction ........................................... 15 2.2 Diastereoselective Directed ortho-Metalation of Ferrocenes with Chiral Auxiliaries ..................... 19 2.3 Enantioselective Directed ortho-Metalation of Ferrocenes with Chiral Bases ........................... 36 2.4 Enzymatic and Nonenzymatic Kinetic Resolutions ......... 40 2.5 Summary and Perspectives ............................... 42 2.6 Selected Experimental Procedures ....................... 44 References .................................................. 49 3 Monodentate Chiral Ferrocenyl Ligands ....................... 55 Ji-Bao Xia, Timothy F. Jamison, and Shu-Li You 3.1 Introduction ........................................... 55 3.2 Nickel-Catalyzed Asymmetric Reductive Coupling Reactions .............................................. 55 3.3 Copper(I)-Catalyzed Asymmetric Allylic Alkylation Reactions .............................................. 62 3.4 Asymmetric Suzuki-Miyaura Reactions .................... 64 3.5 Addition of Organoaluminum to Aldehydes and Enones ..... 65 3.6 Asymmetric Nucleophilic Catalysis ...................... 66 3.7 Conclusion and Perspectives ............................ 70 References .................................................. 70 4 Bidentate 1,2-Ferrocenyl Diphosphine Ligands ................ 73 Hans-Ulrich Blaser and Matthias Lotz 4.1 Introduction ........................................... 73 4.2 Type A Both PR2 Groups Attached to the Cp Ring ......... 74 4.3 Type В One PR2 Group Attached to the Cp Ring, one PR2 Group Attached to the α-Position of the Side Chain ..... 75 4.4 Type С One PR2 Group Attached to the Cp Ring, one PR2 Group Attached to the R-Position of the Side Chain ..... 83 4.5 Type D, One PR2 Group Attached to the Cp Ring, One PR2 Group Attached to Other Positions of the Side Chain .................................................. 85 4.6 Type E, Both PR2 Groups Attached to Side Chains ........ 87 References .................................................. 91 5 1,2-P,N-Bidentate Ferrocenyl Ligands ........................ 97 Yong Gui Zhou and Xue Long Hou 5.1 Introduction ........................................... 97 5.2 Asymmetric Hydrogenation and Asymmetric Transfer Hydrogenation .......................................... 97 5.3 Formation of a C-C Bond ............................... 121 5.4 Cycloaddition Reactions ............................... 132 5.5 Miscellaneous Reactions ............................... 137 5.6 Conclusion and Perspectives ........................... 140 5.7 Experimental: Selected Procedures ..................... 140 References ................................................. 144 6 N,0-Bidentate Ferrocenyl Ligands ........................... 149 Anne Nijs, Olga García Mancheño, and Carsten Bolm 6.1 Introduction .......................................... 149 6.2 Addition of Organozinc Reagents to Aldehydes .......... 149 6.3 Addition to Aldehydes with Boron Reagents ............. 165 6.4 Other Transformations: Asymmetric Epoxidation ......... 168 6.5 Conclusion and Perspectives ........................... 169 6.6 Experimental: Selected Procedures ..................... 170 References ................................................. 173 7 Symmetrical 1,1'-Bidentate Ferrocenyl Ligands .............. 175 Wanbin Zhang and Delong Liu 7.1 Introduction .......................................... 175 7.2 Symmetrical l,l'-Disubstituted Ferrocenyl Ligands ..... 177 7.3 Symmetrical l,l',2,2'-Tetrasubstituted Ferrocenyl Ligands ............................................... 193 7.4 Analogs of Ferrocenes: Symmetrical l,l'-Bidentate Ruthenocenyl Ligands .................................. 203 7.5 Conclusion and Perspectives ........................... 208 7.6 Experimental: Selected Procedures ..................... 208 References ................................................. 211 8 Unsymmetrical 1,1-Bidentate Ferrocenyl Ligands ............. 215 Shu-Li You 8.1 Introduction .......................................... 215 8.2 Palladium-Catalyzed Asymmetric Allylic Substitution Reaction .............................................. 215 8.3 Gold or Silver-Catalyzed Asymmetric Aldol Reactions ... 229 8.4 Asymmetric Hydrogenation .............................. 234 8.5 Asymmetric Cross-Coupling Reaction .................... 239 8.6 Asymmetric Heck Reaction .............................. 242 8.7 Miscellaneous ......................................... 244 8.8 Conclusion and Perspectives ........................... 250 8.9 Experimental: Selected Procedures ..................... 250 References ................................................. 253 9 Sulfur- and Selenium-Containing Ferrocenyl Ligands ......... 257 Juan C. Carretero, Javier Adrio, and Marta Rodríguez Rivero 9.1 Introduction .......................................... 257 9.2 Asymmetric Allylic Substitution ....................... 258 9.3 Other Asymmetric Palladium-Catalyzed Reactions ........ 266 9.4 Gold-Catalyzed Reactions .............................. 268 9.5 Asymmetric Reductions ................................. 269 9.6 Asymmetric 1,2- and 1,4-Nucleophilic Addition ......... 270 9.7 Asymmetric Cycloaddition Reactions .................... 272 9.8 Asymmetric Nucleophilic Catalysis ..................... 276 9.9 Conclusion and Perspectives ........................... 277 9.10 Experimental: Selected Procedures ..................... 278 References ................................................. 280 10 Biferrocene Ligands ........................................ 283 Ryoichi Kuwano 10.1 Introduction .......................................... 283 10.2 Trans-Chelating Chiral Bisphosphines: TRAP ............ 284 10.3 2,2-Bis(diarylphosphino)-1,1-biferrocenes: BIFEP ...... 299 10.4 Miscellaneous Biferrocene-Based Chiral Ligands ........ 302 10.5 Conclusion ............................................ 303 References ................................................. 304 11 Applications of Aza- and Phosphaferrocenes and Related Compounds in Asymmetric Catalysis .......................... 307 Nicolas Marion and Gregory C. Fu 11.1 Introduction .......................................... 307 11.2 Background on Aza- and Phosphaferrocenes .............. 308 11.3 Azaferrocenes in Catalysis ............................ 310 11.4 Phosphaferrocenes in Catalysis ........................ 324 11.5 Conclusions ........................................... 333 References ................................................. 333 12 Metallocyclic Ferrocenyl Ligands ........................... 337 Christopher J. Richards 12.1 Introduction .......................................... 337 12.2 Asymmetric Synthesis of Planar Chiral Metallocyclic Complexes ............................................. 339 12.3 Stoichiometric Synthetic Applications of Scalemic Planar Chiral Metallocyclic Complexes ................. 354 12.4 Asymmetric Catalysis with Scalemic Planar Chiral Palladocyclic Complexes ............................... 355 12.5 Conclusion ............................................ 364 References ................................................. 364 A Show Case of the Most Effective Chiral Ferrocene Ligands in Various Catalytic Reactions ............................. 369 A.l Asymmetric Allylic Substitution Reactions ............. 369 A.l.l Copper(I)-Catalyzed Asymmetric Allylic Alkylation Reactions ........................... 369 A.1.2 Palladium-Catalyzed Asymmetric Allylic Substitution Reactions ......................... 370 A.1.3 Generating π-Allyl Palladium Complex Through the Reaction of Allene with Iodobenzene ........ 372 A.1.4 Regioselective Control Concerned with Unsymmetrically 1,3-Disubstituted 2-Propenyl Acetate ........................................ 372 A.1.5 Applications of Palladium-Catalyzed Asymmetric Allylic Substitution Reaction ....... 375 A.2 Asymmetric Aldol Reactions ............................ 375 A.2.1 Gold-Catalyzed Asymmetric Aldol Reactions ...... 375 A.2.2 Silver-Catalyzed Asymmetric Aldol Reactions .... 376 A.2.3 Applications of Gold or Silver-Catalyzed Asymmetric Aldol Reactions ..................... 376 A.3 Asymmetric Cycloaddition Reactions .................... 377 A.3.1 [3 + 2] Cycloaddition Reactions ................. 377 A.3.2 [4 + 2] Cycloaddition Reactions ................. 377 A.3.3 [3 + 2] Cycloaddition Reactions ................. 378 A.3.4 Asymmetric 1,3-Dipolar Cycloaddition of Azomethine Ylides with N-Phenyl Maleimide ....... 378 A.3.5 [3 + 2] Cycloaddition of Alkynes with Azomethine Imines ............................... 378 A.4 Asymmetric Hydrogenation .............................. 379 A.4.1 Asymmetric Hydrogenation of Alkenes (C = C) .... 379 A.4.2 Asymmetric Hydrogenation of Alkenes (or C = N) ......................................... 383 A.4.3 Asymmetric Hydrogenation of Ketones (C = 0) .... 384 A.4.4 Asymmetric Hydroboration ....................... 385 A.4.5 Asymmetric Hydrosilylation Reaction ............ 385 A.4.6 Asymmetric Transfer Hydrogenation .............. 386 A.5 Pd-Catalyzed Asymmetric Heck Reaction ................. 386 A.6 Addition of Organozinc Reagents ....................... 387 A.6.1 Addition of Dialkylzinc to Aldehydes ........... 387 A.6.2 Addition of Diarylzinc to Aldehydes ............ 388 A.6.3 Addition of Dialkylzinc to C=N Bond ............ 388 A.6.4 Addition of Phenylacetylene to Aldehydes ....... 389 A.6.5 Addition to Aldehydes with Boron Reagents ...... 389 A.7 Asymmetric Rearrangement of Allylic Imidates .......... 390 A.7.1 Rearrangement of N-Arylbenzimidates ............ 390 A.7.2 Rearrangement of N-Aryl-trifluoracetimidate .... 390 A.7.3 Rearrangement with Added Nucleophiles .......... 391 A.8 Cu-Catalyzed Cyclopropanation ......................... 391 A.8.1 With Diphenylethene ............................ 391 A.8.2 With Aryl, Alkyl or Silylethene ................ 391 A.9 Coupling Reaction of Vinyl Bromide and 1-Phenylethylzinc Chloride ............................ 392 A.10 Enantioselective Intramolecular Aminopalladation ...... 392 A.11 Nickel-Catalyzed Asymmetric Three-Component Coupling of Alkynes, Imines, and Organoboron Reagents .......... 392 A.12 Reactions with Ketenes ................................ 393 A.12.1 O-Acylation with Ketenes ....................... 393 A.12.2 Kinetic Resolution by O-Acylation .............. 393 A.12.3 N-Acylation with Ketenes ....................... 394 A.12.4 Kinetic Resolution by N-Acylation .............. 394 A.12.5 C-Acylation via Rearrangement .................. 394 A.12.6 Cycloadditions ................................. 395 A.12.7 Copper-Catalyzed Insertions of Diazo Compounds ...................................... 395 A.12.8 Copper-Catalyzed Cycloadditions ................ 395 A.13 Ring Opening Reaction ................................. 396 A.13.1 Desymmetrization by Halogenations .............. 396 A.13.2 Ring Opening of Bicyclic Alkenes ............... 396 Index ...................................................... 397